JP2003533865A - Method of wet processing an electronic component using an ozone-containing process fluid in the manufacture of the electronic component - Google Patents

Abstract

  (57) [Summary] The present invention is directed to a method of wet processing electronic components using an ozone-containing process fluid. In the method of the present invention, the electronic component is brought into contact with a wetting solution and then with an ozone-containing process fluid containing gaseous ozone. The contacting of the electronic component with the ozone-containing process fluid is performed in the presence of a base. The method of the present invention is particularly useful when attempting to remove organic material from the surface of an electronic component.

Description

Detailed Description of the Invention

(Cross Reference to Related Applications) This application is provisional US application serial number 60 filed July 29, 1998.
/ 094,545, the disclosures of which are incorporated herein by reference in their entirety.

FIELD OF THE INVENTION The present invention relates to electronic components (
Wet processing of electronic components in the manufacture of electronic component precursors)
It is aimed at a method of cessing). More specifically, the present invention relates to methods of treating electronic components using ozone-containing process fluids.

BACKGROUND OF THE INVENTION The wet processing of electronic components such as semiconductor wafers, flat panels and other electronic component precursors during the manufacture of integrated circuits is widely used.
Semiconductor manufacturing is described in P. Gise et al., Semiconductor and I
Integrated Circuit Fabrication Techni
ques (Reston Publishing Co. Reston, Va.
1979) (the disclosure of which is incorporated herein by reference in its entirety)
Etc. are generally described in.

Wet processing is preferably used when preparing electronic components for the purpose of performing processing steps such as diffusion, ion implantation, epitaxy growth, chemical vapor deposition and hemispherical silicon grain growth, or a combination thereof. Be implemented. During wet processing, the electronic components are contacted with a series of processing solutions. For example, when the electronic component is etched, the photoresist is removed, the electronic component is cleaned, an oxide layer is grown, or when the electronic component is rinsed. A solution may be used. For example, US Pat. No. 4,577,650 assigned to the common assignee;
4,740,249; 4,738,272; 4,856,544; 4,633,893;
4,778,532; 4,917,123, and EP 0 233.
184, and Burkman et al., Wet Chemical Procedures.
ses-Aqueous Cleaning Processes, 111-1
51 pages Handbook of Semiconductor Wafer
Cleaning Technology (Werner Kern editor, No
yes Publication Parkridge (New Jersey)
, 1993), the disclosures of which are incorporated herein by reference in their entirety.

There are many types of equipment available for wet processing. For example, a single tank device that is hermetically sealed to the environment (eg, a Full-Flow ™ device supplied by CFM Technologies, Inc.), a single tank device that is open to the environment, or open to the atmosphere. The electronic components can be processed using, for example, a multi-open bath apparatus (eg, a wet bench) equipped with multiple baths as described.

After undergoing the treatment, the electronic component is typically dried. Drying of semiconductor substrates can be carried out using different methods, the goal being to ensure that no contamination is introduced during the drying process. Drying methods include evaporation, centrifugal force using a spin-rinser-dryer, vapor or chemical drying of wafers, for example US Pat. No. 4,778.
, 532 and 4,911,761.

An important consideration for the effectiveness of a wet processing method is that the electronic components processed by the method are extremely clean (ie, minimal particle contamination and minimal chemical residue). Be limited). The very clean electronic component preferably has a smooth surface and a hydrogen-terminated surface without particle, metal, organic or native oxide contamination. Although wet processing methods have been developed with the aim of providing relatively clean electronic components, the complexity associated with technological advances in the semiconductor industry is constantly in need of improvement. One of the most challenging problems when trying to get a very clean product is photoresist removal.

The use of ozone for the purpose of removing organic materials such as photoresists from semiconductor wafers has been investigated. For example, US Pat. No. 5,464,480 issued to Matthews (hereinafter "Matthews" herein) describes a semiconductor wafer at a temperature of about 1 ° C. to about 15 ° C. in a solution containing ozone and water. The method of contacting with is described. Matthews, for example, puts a semiconductor wafer in a tank containing deionized water and maintains the temperature of the water in the range of about 1 ° C. to about 15 ° C. while ozone is derived from the wafer in the deionized water. It is disclosed that the wafer is rinsed with deionized water after it has been diffused for a time sufficient to be oxidized. Matthews also discloses exposing the wafer to ultraviolet light during the process.

Various other methods of using ozone with water for the purpose of removing organic materials from the surface of semiconductor wafers or rinsing the wafers after chemical treatment have also been investigated. For example, in some such methods, ozone gas is generated in an ozone generator and fed to an ozonator to mix the ozone gas with DI water. At the same time, this ozone gas is also supplied to the bottom of the processing tank by a device with a special design (designed to send a uniform flow of gaseous ozone into the bath). Matthews et al., Mat. Res. Soc. Symp. Proc., 1
997, 477, 173-78. In addition, 1997 Joint Int's M
ig. of Electro. Chem. Soc'y and Int'l S
oc'y. Submissions submitted by Kenens et al. at Of Electro., (Ab
(Struct 1886, page 2169), submissions submitted by Wolke et al. (Ab
(Struct 1887, page 2170), Fukazawa et al. submission (Abstract 1892, page 2176), Kashkouush et al. (Abstract 1934, page 2236), Li et al., Submission (Abstract 1890, page 2173). ), Submissions submitted by Joo and others (
Abstract 1891 page 2174), Ultra Clean Pro.
cessing of Silicon Surfaces UCPSS '9
6, Kenens et al., Removal of Organic Contami
nation From Silicon Surfaces. 107-110
See also page.

In another method, the use of ozone injected into ultrapure water (ozone concentration of about 1-2 ppm) is applied to the RCA cleaning method. This ozone content
d) Remove organic impurities with water. Next, the wafer is treated with NH ₄ OH and H ₂ O ₂ to remove organic substances and metal particles, and then the treatment with HF and H ₂ O ₂ removes the inherent oxides and metals. Improves surface smoothness. The wafer is then rinsed with DI water. Ozone gas is generated by electrolysis of ultrapure water. Next, the generated ozone gas is passed through a membrane and dissolved in ultrapure water. Ohmi et al. Electrochem. Soc'y, 140, 1993,
804-10.

Another method uses a moist ozone gas phase. In this way,
The quartz container is filled with a small amount of liquid, but enough to immerse the O ₃ diffuser. This liquid is DI water, optionally supplemented with additives such as hydrogen peroxide or acetic acid. The container is covered and the liquid is heated to 80 ° C. Place wafers just above the surface of this liquid to prevent them from submersing in the liquid. Exposure of the wafer to a moist ambient O ₃ environment is accomplished by sealing the vessel, heating the liquid and continuously blowing O ₃ into the liquid. De Gen
di et al., Symp. VLSI Tech Dig. Tech. Papers, 1
998,168-69. The De Gendt article also describes a method in which 7 liters of liquid may be placed in a quartz tank, an ozone diffuser may be located at the bottom of the tank and the liquid heated. A wafer is located just above the ozone diffusing device and immersed in the liquid so that O ₂ / O ₃ bubbles come into contact with the surface of the wafer. OH for De Gendt's paper
It has also been reported that the process efficiency can be improved by using a group scavenger such as acetic acid.

Another method involves removing the photoresist in a vapor phase reactor at temperatures in the range of about 200-300 ° C. In certain cases, ozone gas is mixed with an additive such as N ₂ O gas. See Olness et al., Mat. Res. Soc'y. S
ymp., 135, 1993, 261-66.

In addition, spin cleaning using ozone-containing water
g) Technology was also investigated. For example, Cleaning Technology In
Semiconductor Device Manufacturing
Symposium, Yonekawa et al., Contamation Re
move By Wafer Spin Cleaning Process
With Advanced Chemical Distribution
System, 94-7, 94-101; 1997 Joint Int's.
Mtg. of Electro. Chem. Soc'y and Int'l
Soc'y of Elctro. Submitted by Osaka et al. (Abs
See tract 1888, page 2171).

The use of ozone with cleaning solutions was also investigated. One such method involves single-wafer spin with ozone-containing water and dilute HF for the purpose of removing contaminants such as particles, metallics and organics from the wafer surface. A wafer cleaning procedure is used. Such a method consists of pouring ozone-containing water onto the surface of the wafer for 10 seconds and then diluting HF onto the wafer for 15 seconds.
This cycle is repeated until the desired result is achieved. 19
97 Joint Int's Mtg. of Electro. Chem. S
oc'y and Int'l Soc'y. of Elctro. At Tsut
Submissions submitted by Omu et al. (Abstract 1888, page 2171), and also submissions by Han et al. (Abstract 1889, page 2172),
Submissions submitted by Fukazawa et al. (Abstract 1892-2176)
Page), Ultra Clean Processing of Silicon
Surfaces UCPSS '96, Kenennes et al., Removal
of Organic Continuation From Silic
See also on Surfaces, pages 107-10.

In addition, a semiconductor wafer was also cleaned using gaseous ozone and other chemicals such as hydrofluoric acid and hydrochloric acid for the purpose of removing contaminated residual particles. For example, US Patent No. 5,181,985 to Lampert et al. ("Lam
"pert") is sprayed with water on a semiconductor wafer at a temperature of 10 ° C to 90 ° C and a chemically active gaseous substance such as ammonia, hydrogen chloride, ozone, ozone-containing oxygen, chlorine or bromine is introduced. A cleaning method is disclosed. Lampe
rt uses ozone or ozone-containing oxygen to generate an oxide on the surface and then removes it with hydrofluoric acid or hydrochloric acid.

It has also been practiced to use ozone with sulfuric acid as a means of removing photoresist from semiconductor wafers. See, for example, U.S. Pat. Nos. 4,899,767 and 4,917,123 issued to CFM Technologies. The method described in this CFM patent is carried out using a single tank apparatus, and it is common practice to add an oxidizing agent such as ozone to a sulfuric acid solution. Another device that uses sulfuric acid with ozone is a super jar plate that has holes to disperse the gas into the bath in the tank.
It is possible that a gas dispersion device containing a plate) is used. See, for example, US Pat. No. 5,082,518 assigned to SubMicron. The SubMicron patent describes the use of a device to disperse ozone directly into a treatment tank containing sulfuric acid.

Ozone ashing has also been investigated as a means of removing photoresist material from wafers. In such a method, two types of strongly oxidizing gases, ozone and atomic oxygen are used to oxidize the photoresist at a higher temperature (250-350 ° C.). The presence of a small amount of excited nitrous oxide increases the ashing rate. Olness et al., Mat. Res. Soc '
y. See Symp., 135, 1993, 261-66.

US Pat. No. 5,503,708 to Koizumi et al. (“Koizumi”)
Discloses an alternative apparatus and method that uses gaseous ozone for the purpose of removing the photoresist film from a semiconductor wafer. Koizumi uses an apparatus that processes a single wafer at a time. Using this apparatus, the wafer surface is contacted with a gas mixture containing ozone and alcohol while heating the wafer surface, preferably to a temperature of 150 ° C. to 250 ° C., for the purpose of achieving photoresist removal.

It has also been sought to use ozone in the pre-cleaning step. In one such method, such as the method disclosed in McNeilly et al., US Pat. No. 5,762,755, organically contaminated wafers are heated to at least 200 ° C. by radiation while being held under some vacuum. After that, it is contacted with ozone. Next, the wafer is cooled to a temperature of 80 ° C. or lower, and then contacted with ultraviolet-excited chlorine.

Another method of pre-cleaning the wafer is an etch repeatability (etch rep
oxide etching (o
The O ₃ / IR method has been used as an in-situ cleaning step to remove organics by conditioning the surface prior to xide etching). A thin oxide layer may be grown on the surface of the wafer as a post-treatment step. In such a method, ozone is fed into the process chamber while the wafer is heated to a specific temperature by an infrared lamp, the supply of ozone is stopped, and the wafer is cooled with an inert gas at a low temperature. It is being appreciated. Cleaning Technology In Semico
ndevice Device Manufacturing Symposi
um, Kao et al., Vapor-Phase pre-Cleans for F
urnace-Grown and Rapid-Thermal Thin
Oxides, 1992, 251-59.

The use of ozone gas in cooperation with UV light for cleaning and etching the wafer surface was also investigated. Semiconductor Wafer Cle
aning and Surface Characterization (Minute of the Second Workshop), Moon, Si Wafer Cleaning Study
y by UV / Ozone and In Situ Surface A
analysis, 68-76; ASM Int'l, Li et al., UV / Ozone.
Pre-Treatment on Organic Cominate
d Wafer for Complete Oxide Removal H
See F Vapor Cleaning.

Although the use of ozone for use in wet processing technology has been investigated,
There are still many drawbacks. For example, one problem associated with the use of ozone dissolved in water is that ozone has a very low mass transfer rate towards electronic components. In addition, when ozone is dissolved in water, it decays very quickly. Such ozone decay can even be accelerated by factors such as increasing the pH of the solution. Therefore, there is a need to provide ozone that can be easily transported in a stable form to the surface of electronic components.

Gaseous ozone has been used alone and in combination with other gaseous substances for the purpose of improving the processing speed of electronic components, but the use of gaseous ozone likewise has drawbacks. Have. For example, gaseous ozone often leaves undesired oxidized organic by-products on the electronic components that need to be removed later, often requiring additional equipment. Moreover, the temperatures of the treatments carried out, especially for the purpose of removing the photoresist, are typically high (above 150 ° C., more generally above 250 ° C.). Such high temperatures can lead to malfunctioning electronic components. Another drawback is that many devices currently used when processing electronic components with gaseous ozone are devices that process a single wafer at a time and / or have several processing steps in one. It is not a device that allows it to be carried out in a bath.

Accordingly, there is a need in the art for a simple and efficient method that allows for the safe chemical treatment of electronic components with ozone while at the same time providing an environmentally safe and economical way. ing.

The present invention satisfies not only such needs, but also other needs.
For example, the present invention provides a method that facilitates the stable delivery of ozone to electronic components during wet processing. The present invention also provides a method of contacting an electronic component with gaseous ozone and other processing solutions in a series of steps, for example in a single bath.

SUMMARY OF THE INVENTION The present invention provides, among other things, a method of wet processing electronic components in the manufacture of electronic components, including electronic component precursors such as semiconductor wafers used in integrated circuits. It is a thing. More specifically, the present invention relates to methods of processing electronic components using, for example, wet processing techniques with ozone-containing process fluids. In particular, the method of the invention can be used, inter alia, for the purpose of removing organic materials, such as photoresists, from electronic components and oxidizing the surface of electronic components (ie growing an oxide layer). The method of the invention can also be used in pretreatment steps, such as cleaning or etching.

In one aspect of the invention, there is provided a method of wet processing an electronic component, the method comprising the step of wetting a surface of the electronic component.
An ozone-containing process fluid containing gaseous ozone, wherein the surface of the electronic component is wetted with the wetting solution by contacting [wherein the wetting solution contains water], where the ozone is The contained process fluid in the form of a gas, a vapor, a mist or a mixture thereof, and contacting the electronic component with the ozone containing process fluid in a reaction chamber for a contact time [here The temperature of the ozone-containing process fluid is at a temperature of about 20 ° C. to about 145 ° C., at least one base is present during at least a portion of the contacting time, and the base is in the wetting solution or Present in the ozone-containing process fluid or a combination thereof].

Another aspect of the present invention also provides a method for wet processing of electronic components, the method comprising loading a number of electronic components into a single encloseable bath, the electronic components comprising: The surface of the electronic component is wetted with the wetting solution by contacting the surface with a wetting solution, where the wetting solution contains water, and an ozone-containing process fluid containing gaseous ozone [ Where the ozone-containing process fluid is in the form of a gas, vapor, mist or mixture thereof, and the electronic component is contacted with the ozone-containing process fluid in the reaction chamber for a contact time, and After contacting the electronic component with the ozone-containing process fluid, the electronic component is contacted with one or more processing solutions in the bath [wherein Bring the temperature of the ozone-containing process fluid to a temperature of about 20 ° C. to about 145 ° C.,
At least one base is present during at least a portion of the contact time, and the base is present in the wetting solution or in the ozone-containing process fluid or a combination thereof]. Include.

In yet another aspect of the present invention, there is also provided a method of wet processing an electronic component, the method comprising the step of adding the electronic component to a wetting solution [wherein the wetting solution contains water and at least one base. The surface of the electronic component is moistened with the wetting solution by contacting with, and the moistened electronic component is contacted with the ozone-containing process fluid for a contact time [here, the ozone-containing process fluid]. In the form of gas, steam, mist or mixtures thereof, and the temperature of the ozone containing process fluid is about 20
C. to about 145.degree. C.] and contacting the electronic component with gaseous ozone followed by contacting the electronic component with one or more processing fluids.

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method of wet processing electronic components using an ozone-containing process fluid. The method of the present invention is particularly useful for removing organic materials from the surface of electronic components using ozone-containing process fluids. For example, in the method of the present invention, during wet processing, organics such as photoresists (ashed or unashed), plasticizers, surfactants, fluorocarbon polymers, organics derived from human contact or combinations thereof are used. Material can be removed. The method of the invention can also be used to grow oxide layers on the surface of electronic components. It is also contemplated to use the method of the present invention in pre-treatment cleaning, cleaning between processing steps, and post-processing cleaning and processing (eg oxide growth).

The present invention also allows for the simultaneous treatment of multiple electronic components with ozone-containing process fluids and / or subsequent contact of the electronic components with other process fluids in the same bath. A method of using an ozone-containing process fluid is also provided.

As used herein, the term “wet process” or “wet process” refers to one or more liquids of an electronic component for the purpose of treating the electronic component in a desired manner (hereinafter “process liquid”). "Or" process solution "). For example, it may be desirable to process the electronic component for the purposes of cleaning the surface of the electronic component, etching it, or removing photoresist from it. It may also be desirable to rinse the electronic components between such processing steps.

Wet processing may also include the step of contacting the electronic component with another fluid, such as a gas, a vapor, or a liquid mixed with a vapor or gas, or a combination thereof. The term "process fluid" as used herein includes liquids, gases, liquids in the vapor phase, or combinations thereof. As used herein, the term "vapor" refers to liquids that have partially evaporated, saturated vapors, unsaturated vapors,
It is meant to include supersaturated steam or a combination thereof. Term "fog"
As used herein means droplets of droplets. For example, the fog may be droplets in the size range of preferably about 10 μm to about 1500 μm, more preferably about 50 μm or less, most preferably about 30 μm or less.

Various types of process fluids are used during wet processing. The most common types of process fluids used during wet processing are generally reactive chemical process fluids or liquids, and rinsing fluids or liquids. As used herein, the term "reactive chemical process fluid" or "reactive chemical process liquid" refers to any liquid or liquid that reacts with the surface of an electronic component to alter the surface composition of that electronic component in a desired fashion. It is a fluid. For example, the reactive chemical process liquid or fluid may be active in removing contaminants such as particles, metals, photoresists or organic materials that are attached or chemically bound to the surface of the electronic component, or It may be active in etching the electronic component surface or active in oxide layer growth that occurs on the electronic component surface. As used herein, a "rinsing liquid" or "rinsing fluid" is liberated by reactive chemical process fluids, reaction by-products and / or particles or chemical processing steps remaining from electronic components and / or baths. Or DI water or some other liquid or fluid that removes other contaminants that are liberated. Such rinses or fluids can also be used to prevent loose particles or contaminants from redepositing on the electronic components or baths. Examples of reactive chemical process fluids and rinse fluids useful in the method of the invention are described in more detail herein below.

As used herein, “chemical treatment step” or “wet treatment step” refers to contacting an electronic component with a reactive chemical process fluid or process fluid, respectively.

As used herein, the term “reaction chamber” refers to baths (closed or open to atmosphere), baths, wet benches and other storage baths suitable for use in the wet processing of electronic components. The term "single bath" refers to any wet processing apparatus that holds electronic components in one bath throughout the wet processing procedure.

The term “electronic component” as used herein refers to, for example, an electronic component precursor,
For example, semiconductor wafers, flat panels, and electronic components (ie integrated circuits)
Other components used in the manufacture of, such as CD ROM disks, hard drive memory disks or multi-chip modules.

In the method of the present invention, the electronic component is contacted with a wetting solution and an ozone-containing process fluid, wherein at least one base is contacted with the electronic component with the ozone-containing process fluid. Is present for at least part of the contact time. The base may be present, for example, in the wetting solution, in the ozone-containing process fluid, or both.

Without wishing to be bound by theory in any way, it is believed that the presence of a base in the wetting solution and / or the ozone containing process fluid enhances the reaction of ozone with electronic components in the following manner. ing. The presence of a base enhances the formation of hydroxide ions in the presence of a compound having a hydroxyl functional group (eg, ammonia in the presence of water) or a source of hydroxide ions (eg, ammonium hydroxide). Given directly. It is considered that this hydroxide ion reacts with ozone to generate a hydroxyl group. It is believed that such hydroxyl groups are more effective than ozone at removing or oxidizing contaminants such as organic materials found on the surface of electronic components. In particular, the hydroxyl group is typically seen saturated and unsaturated carbon to the organic material - produce CO, CO _2, H ₂ O or such oxidation reaction product of the combination thereof with rapid and non-selectively reacted with carbon bonds I believe. By comparison, gaseous ozone also reacts with organic materials, but the reaction with this gaseous ozone is more selective and slow.

One difficulty in attempting to generate hydroxyl groups is that higher pH reduces ozone stability and, as a result, the presence of a base can actually suppress the formation of hydroxyl groups. is there. Additionally, even if hydroxyl groups occur, their lifetime is very short (eg, a few seconds). Therefore, preferably, the base and ozone are added in a manner that facilitates the formation of hydroxyl groups at or near the surface of the electronic component, as described in more detail herein below.

The wetting solution may be any liquid that contains water and has the ability to wet the surface of the electronic component. “Wet” or “wet” means that when the wetting solution contacts an electronic component, it preferably forms a wetting solution layer over the electronic component. While not intending to be bound by theory in any way, such a layer is such that ozone reacts at or near the surface of the electronic component to form a hydroxyl group and / or reacts directly with the surface of the electronic component. We believe that it will provide an effective medium for Suitably, such a layer of wetting solution is continuous so that ozone can react uniformly on the surface of the electronic component.
The thickness of this layer is preferably relatively thin (eg, preferably about 40) to ensure that ozone reacts sufficiently close to the surface of the electronic component to form hydroxyl groups.
μm or less).

In addition to water, the wetting solution may also contain other compounds (preferably soluble in water) that promote the formation of hydroxyl groups. Such compounds are, for example, hydroxyl functional groups which can give rise to hydroxyl groups in the presence of ozone or water.
nctional groups) may be included. Examples of compounds that facilitate the formation of hydroxyl groups include, for example, hydrogen peroxide, bases or combinations thereof. Bases which may be present in the wetting solution include, for example, inorganic or organic bases such as ammonia, ammonium hydroxide, alkylammonium hydroxides such as trimethylammonium hydroxide, alkali or alkaline earth metal hydroxides. , Organic amines, basic amino acids, or combinations thereof, such as sodium hydroxide or potassium hydroxide. Suitable bases include ammonium hydroxide, alkyl ammonium hydroxide, alkali metal hydroxides, alkaline earth metal hydroxides, or combinations thereof. Suitable amounts of such compounds in the wetting solution will depend on the compound selected. In the case of a base, the base is preferably added in an amount to bring the pH of the wetting solution to about 9 to about 13. In the case of hydrogen peroxide, hydrogen peroxide is preferably present in the wetting solution in an amount of from about 0.01 moles per liter to about 0.5 moles per liter.
Moles, more preferably about 0.05 moles per liter to about 0 per liter.
． Present at a concentration of 2 molar.

The manner in which the electronic component is contacted with the wetting solution may be any manner so long as the surface of the electronic component is wet with the wetting solution. For example, the electronic component may be dipped into and removed from the wetting solution. It is also possible to put the electronic components in a bath, fill the bath with the wetting solution and then drain it. It is also possible to add the wetting solution as a mist to the electronic component. Thus, there are various methods of wetting the electronic component by contacting the wetting solution with the electronic component. Those skilled in the art will recognize that the method of wetting such an electronic component can be varied in order to adjust the thickness of the wetting solution layer produced on the electronic component. For example, the thickness of the layer that occurs on the electronic component when the electronic component is immersed in the wetting solution will be thinner the slower the wetting solution is removed from the electronic component.

The temperature of the wetting solution during contact with the electronic component is preferably about room temperature to about the condensation temperature of the wetting solution. The temperature of the wetting solution may be, for example, about 25 ° C to about 100 ° C, more preferably about 30 ° C to about 80 ° C, most preferably about 35 ° C to about 60 ° C. The pressure of the wetting solution during contact with the electronic components is preferably about 0 pisg to about 20 pisg.

In the method of the present invention, the electronic component is also contacted with the ozone-containing process fluid. The ozone-containing process fluid may be any fluid in the form of a gas, vapor, mist or combination thereof containing gaseous ozone. The ozone-containing process fluid may be, for example, gaseous ozone or a combination of gaseous ozone and one or more other process fluids. Other process fluids present in such ozone-containing process fluids are preferably in the form of steam, gas, mist or combinations thereof. Bringing one or more of such other process fluids into a gas, vapor or mist results in greater stability of the gaseous ozone as compared to when the ozone is dissolved in the liquid, thereby providing a gaseous ozone. There is an increased opportunity for the particles to reach and react with the surface of the electronic component (eg, organic material present on the surface of the electronic component).

The concentration of ozone present in such an ozone-containing process fluid, expressed as the weight of ozone per volume of ozone-containing process fluid at standard temperature and pressure (25 ° C., 1 atmosphere), is preferably about It is from 10 g / m ³ to about 300 g / m ³ , more preferably from about 50 g / m ³ to about 250 g / m ³ , and most preferably from about 100 g / m ³ to about 200 g / m ³ . The temperature of the ozone-containing process fluid contacted with the electronic components will generally depend on the ozone-containing process fluid selected, but the temperature of the ozone-containing process fluid is preferably about 20 ° C to about 145 ° C, It is preferably in the range of about 40 ° C to about 120 ° C. The pressure of the ozone-containing process fluid during contact with the electronic component is preferably about 0 pisg to about 20 pisg.
, More preferably from about 1 pisg to about 10 pisg, most preferably from about 1 pisg to about 5 pisg.

As mentioned above, it is also possible for such ozone-containing process fluids to contain other process fluids in addition to gaseous ozone. In a preferred aspect of the invention, the ozone-containing process fluid contains, for example, a hydroxide fluid. By "hydroxide fluid" is meant any process fluid that facilitates the formation of hydroxyl groups in the presence of ozone, either alone or in combination with other reactants, which forms are gas, vapor, mist or It is a combination of them. Such hydroxide fluid may contain, for example, a compound having a hydroxyl functional group that promotes the formation of hydroxyl groups, or the hydroxide fluid may be a base, or It may be a combination thereof.

Suitable hydroxide fluids include, for example, water, hydrogen peroxide, or bases that alone or in combination with other process fluids, such as water, can provide hydroxide ions, or any combination thereof. Be done. Bases useful in the present invention include inorganic and organic bases. Suitable bases include, for example, ammonia, ammonium hydroxide, alkylammonium hydroxides such as trimethylammonium hydroxide, alkali or alkaline earth metal hydroxides such as sodium hydroxide or potassium hydroxide, organic amines, basic Amino acids, or combinations thereof are included. Suitable bases include ammonia, ammonium hydroxide, trimethyl ammonium hydroxide, organic amines, or combinations thereof.
The most preferred hydroxide fluid useful in the method of the present invention is water, ammonia, ammonium hydroxide, trimethylammonium hydroxide, or a combination thereof.

The concentration of hydroxide fluid in the ozone-containing process fluid will depend on process parameters such as the type of hydroxide fluid used. For example, in the case of a base, the base takes into account that there is some hydroxide fluid from the ozone-containing process fluid attached to the electronic component and water from the wetting solution. And preferably added in an amount such that the surface of the electronic component exhibits a pH of about 9 to about 13. In the case of water and hydrogen peroxide, the molar ratio of ozone to hydroxide fluid is preferably about 1:90 to about 40: 1, more preferably about 1:10 to about 20: 1, and most preferably Should be about 1: 2 to about 2: 1.

In addition to such hydroxide fluids, other process fluids can be present in the ozone-containing process fluid. Examples of other process fluids include, for example, alcohols such as C ₁ to C ₂₀ alcohols, more preferably C ₁ to C ₆ alcohols such as methanol, ethanol, propanol (eg isopropanol).
, Butanol, pentanol or hexanol, hydrogen chloride, hydrogen fluoride,
Carbon dioxide or a combination thereof is included. Since acetic acid is a hydroxyl-capturing agent, it is preferable to substantially remove acetic acid from the reaction chamber for the purpose of preventing the hydroxyl group from being captured when gaseous ozone is present in the reaction chamber. Such other process fluid is added to the ozone-containing process fluid such that the molar ratio of ozone in the ozone-containing process fluid to the other process fluid is preferably about 1:90 to about 40.
It may be present in an amount of 1: 1.

The preferred temperature of the process fluid (eg, hydroxide fluid or other process fluid) prior to producing the ozone-containing process fluid will depend on the morphology of the process fluid. For example, if the process fluid is a gas such as ammonia, preferably the process fluid is not heated prior to forming the ozone containing process fluid. If the process fluid is a mist, the temperature of the process fluid is preferably in the range of about room temperature to the condensation temperature of the process fluid. In the case of water, its temperature is preferably about 20 ° C to about 100 ° C. When the process fluid is steam, it is preferably at a temperature above its condensation temperature, more preferably at a temperature at which the steam can condense on the surface of the electronic component. In this regard, the temperature of the electronic component may be at or slightly below the condensation temperature of the vapor so as to improve condensation, such as above 20 ° C. May be desirable.

There are a variety of methods that make it possible to produce such ozone-containing process fluids. This production method is preferably a method that does not significantly promote the deterioration of ozone. For example, by adding each process fluid to a reaction chamber containing individually moistened electronic components before or during the addition of gaseous ozone, etc.
An ozone-containing process fluid can be produced. It is also possible to produce an ozone-containing process fluid through combining ozone and / or any process fluid prior to adding them to the reaction chamber containing the electronic components. Where it is desired to combine ozone and any process fluids prior to adding them to the reaction chamber, the morphology of such process fluids is preferably such that the reaction of them with ozone is minimized. Form. For example, if it is desired to combine gaseous ozone and a base prior to entering the reaction chamber, then said base is preferably a gas, such as ammonia,
This is because the ozone reaction is slower in the gas than in the fog or steam. For the purpose of avoiding the risk of ozone degradation, ozone is preferably added to the reaction chamber separately from the other process fluids to produce an ozone containing process fluid.

Further, for the purpose of improving the degree to which the hydroxyl group is generated on the surface of the electronic component, it is possible to add the components to be included in the ozone-containing process fluid in an alternating order. For example, in a preferred embodiment of the present invention, the addition of the process fluid to be included in the ozone-containing process fluid is done shortly before and optionally during the addition of gaseous ozone. Following such a procedure, the electronic components are coated with a thin layer of one or more process fluids (eg, water and / or base), which makes it more likely that ozone will react in this layer to form hydroxyl groups. Can be. Another advantage of such a method is that gaseous ozone is not given the opportunity to react with the process fluid contained in the ozone-containing process fluid before it reaches the surface of the electronic component.

Described herein are some specific embodiments of producing an ozone-containing process fluid in accordance with the method of the present invention. Such embodiments are provided by way of example only and are not intended to limit the scope of the invention in any way.

In one aspect of the invention, gaseous ozone and water vapor may be combined under pressure to produce an ozone-containing process fluid. The ozone-containing process fluid can then be expanded into the reaction chamber, such as through a throttle valve, which can expand.

In another aspect of the present invention, the gaseous ozone and hydroxide fluid are added to the reaction chamber containing the electronic components through separate openings and combined together in the reaction chamber. A process fluid may be generated. When the gaseous ozone and the hydroxide fluid are added separately, they may be supplied, for example, through openings located on the opposite side, for the purpose of increasing the degree to which hydroxyl groups are generated on the surface of the electronic component.

In another aspect of the invention, the ozone and the mist are sprayed into the reaction chamber with a hydroxide fluid in the form of a mist before and / or during the addition of gaseous ozone to the reaction chamber. The gaseous ozone and hydroxide fluid may be combined through combination in the reaction chamber. The fog may be a fog produced by any technique known to those skilled in the art, such as ultrasound or megasonic.
A sonic) atomizer, jet, atomizer or spray nozzle may be used to generate the mist. In a preferred embodiment, the gaseous ozone is added to the bottom of the reaction chamber and the hydroxide fluid is added from the top of the reaction chamber. The mist may be, for example, a mist of deionized water or a mist of a base dissolved in water.

Suitably, the mist is supplied to the reaction chamber at a temperature below the condensation temperature of the hydroxide fluid. For example, in the case of a mist of deionized water or a base dissolved in water, the temperature is preferably about 25 ° C to about 90 ° C, more preferably about 30 ° C to about 50 ° C. The ozone is preferably at a temperature of about 25 ° C to about 50 ° C and about 1
Feed the reaction chamber at a pressure of about 20 pisg from pisg. One advantage of using an ozone containing process fluid containing a mixture of a mist of hydroxide fluid and gaseous ozone is that ozone has a longer life in the mist than ozone in bulk liquid (bu).
It is longer than the life shown in the state of being dissolved in lk liquid) and longer than the life shown in the state where ozone is mixed with high-temperature (for example, more than 90 ° C.) steam.

In another aspect of the invention, the ozone containing process fluid may be produced from ozone containing water. Ozone-containing water is produced by dissolving gaseous ozone in a solution containing water according to techniques well known to those skilled in the art. For example, the dissolution of ozone is carried out at a temperature and pressure that enhances the solubility of ozone in water. The ozone-containing water is then subjected to a treatment, such as by evaporating the ozone-containing water to produce an ozone-containing process fluid containing ozone and water vapor.

After dissolving the ozone, the ozone-containing water may be treated to produce an ozone-containing process fluid in various ways. For example, in one aspect, heating may be used to evaporate the ozone containing process liquid to produce an ozone containing process fluid containing ozone and water vapor.

In another embodiment, the ozone containing water is contacted with a carrier gas such as nitrogen. The carrier gas preferably "picks up" or vaporizes gaseous ozone and water vapor to produce an ozone-containing process fluid containing the carrier gas, ozone and water vapor.
Contacting the carrier gas with the ozone-containing process liquid may be performed using any technique known to those skilled in the art, such as sparging or bubbling the carrier gas into the ozone-containing process liquid. bubblin
g) and the like. The temperature of the carrier gas during the contact with the ozone-containing water is preferably lower than the boiling point of the ozone-containing water.

After the ozone-containing process fluid is created, it is preferably immediately contacted with the electronic components contained in the reaction chamber for a time suitable to achieve the desired result. The temperature of the electronic components during this contact is preferably at or slightly below that of the ozone-containing process fluid. As used herein, "contact time" means the time that an electronic component is in contact with a process fluid. This contact time is, for example, the time during which the electronic component is in contact with the process fluid while the tank is being filled with the process fluid, or the electronic component is immersed in the process fluid. It will include the time of immersion in the chamber and the time the electronic component is in contact with the process fluid while removing the process fluid or electronic component from the bath. Also, the contact time actually selected will depend on such variables as the temperature, pressure and composition of the ozone-containing process fluid, and the composition of the surface of the electronic component. The contact time with such an ozone-containing process fluid is preferably at least 30 seconds.

Contacting with this ozone-containing process fluid is preferably carried out after wetting the electronic component with the wetting solution in order to ensure that a layer of the wetting solution is present on the electronic component. To do. However, as long as the electronic component is wet with the wetting solution before ozone has finished flowing into the reaction chamber, the electronic component is in contact with the wetting solution such that the electronic component is in contact with the ozone-containing process fluid. It is also possible to do it simultaneously for at least part of the time.

As mentioned above, contact between such an ozone-containing process fluid and the electronic component is effected in the presence of at least one base, wherein the base is present in the ozone-containing process fluid. (E.g., as the hydroxide fluid described above), or in the wetting solution, or in both the ozone-containing process fluid and the wetting solution. If it is desired to keep the base in the ozone-containing process fluid, it is preferably described above to minimize the extent to which the base degrades the ozone before it reaches the surface of the electronic component. The base is combined with gaseous ozone according to the method described above.

There are a variety of methods that allow contacting the electronic component and the ozone-containing process fluid in the presence of a base during at least a portion of the contact time during which the electronic component is in contact with the ozone-containing process fluid. is there. Some specific embodiments of contacting the ozone containing process fluid with the electronic component in the presence of a base are described herein. Such embodiments are provided by way of example only and are not intended to limit the scope of the invention in any way. In one aspect of the invention, the electronic component is contacted with a wetting solution containing water and then with an ozone containing process fluid containing gaseous ozone, water vapor and a base. The base in this embodiment is preferably a gas, a vapor or a combination thereof, which is selected from ammonia, alkylammonium hydroxide, organic amines or combinations thereof, most preferably ammonia. Suitably, the ozone-containing process fluid is produced through the separate addition of ozone, water vapor and ammonia to the reaction chamber. Preferably, deionized water vapor is applied at a pressure of about 1 psig to about 20 psig and at about 70 ° C to about 140 ° C.
Supply at the temperature of. Ozone and ammonia are preferably about 1 pisg to about 20 pi
Feed at a temperature of about 25 ° C. to about 50 ° C. under pressure in the range of sg.

In another aspect of the invention, a base dissolved in an ozone-containing process fluid containing ozone and an aqueous solution after contacting the electronic component with a wetting solution containing water, which base may be, for example, hydroxylated. Ammonium or an aqueous solution containing an alkali or alkaline earth metal hydroxide). In this embodiment, the base is preferably added to the reaction chamber as a flow mist separate from ozone.

In a preferred embodiment of the present invention, the electronic component is contacted with a wetting solution containing a base (hereinafter “basic solution”) and then with an ozone-containing process fluid. The basic solution preferably includes a solution containing ammonium hydroxide or a hydroxide of an alkali or alkaline earth metal. The ozone-containing process fluid may be, for example, high purity gaseous ozone or a mixture of hydroxide fluid (eg water and / or base) and ozone.

There are various ways in which it is possible to supply the basic solution and the ozone-containing process fluid to the reaction chamber in this manner. For example, the basic solution may be delivered to the reaction chamber in the form of a fog before or during the addition of the ozone-containing process fluid to the reaction chamber. It is also possible to add the basic solution to the electronic component through filling the reaction chamber containing the electronic component with the basic solution. In this aspect, ozone-containing process fluid may be added to the reaction chamber during or after removal of the basic solution from the reaction chamber (eg, through direct replacement of the basic solution with ozone-containing process fluid). Good.

In another preferred embodiment of the invention, the electronic component is contacted with a wetting solution that is a mist of water and the electronic component is contacted during and / or after the contacting of the electronic component with the wetting solution. The component is contacted with an ozone containing process fluid containing ammonia and gaseous ozone. In this aspect, the gaseous ozone and ammonia are preferably added separately to the reaction chamber.

In addition to contacting the electronic component with the ozone-containing process fluid,
It may be contacted with any number of other reactive chemical process fluids (eg, gas, liquid, vapor or any combination thereof) for the purpose of achieving the desired result. For example, the electronic component may be a reactive chemical process fluid used in etching (hereinafter referred to as an etching fluid), a reactive chemical process fluid used in growth of an oxide layer (hereinafter referred to as an oxidation fluid). A material growth fluid), a reactive chemical process fluid used to remove photoresist (hereinafter referred to as photoresist removal fluid), and a reactive chemical process fluid used to improve cleaning (herein described). Hereinafter referred to as a cleaning fluid), or a combination thereof. It is also possible to rinse the electronic components with a rinsing fluid, which can be done at any time during the wet processing method. Preferably, such reactive chemical process fluids and rinsing fluids are liquid.

Reactive chemical process fluids useful in the present invention are fluids containing one or more chemically reactive agents such that the desired surface treatment is achieved. The concentration of such chemically reactive agent is preferably 1 based on the weight of the reactive chemical process fluid.
The concentration is more than 000 ppm, more preferably more than 10,000 ppm. However, in the case of ozone, its concentration is generally equal to or greater than about 10 ppm, more preferably about 10 ppm to about 50 ppm. Examples of chemically reactive agents are, for example, hydrochloric acid or buffers containing hydrochloric acid, ammonium hydroxide or buffers containing ammonium hydroxide, hydrogen peroxide, sulfuric acid or buffers containing sulfuric acid, mixtures of sulfuric acid and ozone, hydrofluoric acid. Or hydrofluoric acid-containing buffer, chromic acid or chromic acid-containing buffer, phosphoric acid or phosphoric acid-containing buffer, acetic acid or acetic acid-containing buffer, nitric acid or nitric acid-containing buffer, ammonium fluoride as a buffer Included are hydrofluoric acid, deionized water, ozone, and the like, or combinations thereof.

Also, such a reactive chemical process fluid may contain one or more chemically reactive agents.
It is also possible to contain 00%. For example, it may be desirable to contact the electronic component with a solvent such as acetone, N-methylpyrrolidone or combinations thereof. Such solvents are, for example, chemically reactive agents used to remove organics or to provide other cleaning benefits.

Examples of suitable reactive chemical process fluids useful in the present invention include cleaning fluids, etching fluids and photoresist removal fluids. The cleaning fluid is typically a fluid containing one or more corrosive agents such as acids or bases. Suitable acids for the cleaning fluid include, for example, sulfuric acid, hydrochloric acid, nitric acid or aqua regia. Suitable bases include, for example, ammonium hydroxide. The desired concentration of corrosive agents in such cleaning fluids will depend on the particular corrosive agent selected and the degree of cleaning desired. Such corrosive agents can also be used with oxidants such as ozone or hydrogen peroxide. Suitable cleaning solutions are the "SC1" solution containing water, ammonia and hydrogen peroxide, and the "SC2" solution containing water, hydrogen peroxide and hydrochloric acid. H ₂ O for SC1 solution:
A typical concentration range of H ₂ O ₂ : NH ₄ OH is from about 5: 1: 1 to about 200: 1: 1 :.
It is a volume part. A typical concentration range of H ₂ O: H ₂ O ₂ : HCl for SC2 solution is from about 5: 1: 1 to about 1000: 0: 1: parts by volume. A suitable etching solution is a solution containing an agent that has the ability to remove oxides. Typical etchants used are, for example, hydrofluoric acid, hydrofluoric acid with buffers, ammonium fluoride, or other substances that produce hydrofluoric acid in solution. The H ₂ O: HF content of the etching solution containing hydrofluoric acid may range, for example, from about 4: 1 to about 1000: 1 parts by weight.

Those skilled in the art will recognize that there are a variety of process fluids that can be used during wet processing. Another example of a process fluid that can be used during wet processing is "Ch
electrical Etching ”by Werner Kern et al., Thin
Film Processes, John L. Edited by Vosser and others, Aca
disclosed by Dem Press (NY) Publication, 1978, pages 401-496, which is incorporated herein by reference in its entirety.

It is also possible to contact said electronic component with a rinsing fluid while carrying out the method of the invention. As mentioned above, removing residual reactive chemical process fluids, reaction byproducts, and / or particles or other contaminants liberated by chemical processing steps from electronic components and / or vessels. A rinsing fluid is used for this purpose. The rinsing fluid can also be used to prevent the loose particles or contaminants from redepositing on the electronic component or bath.

Any rinsing fluid that can achieve the effects described above can be selected. When selecting a rinsing fluid, the nature of the electronic component surface to be rinsed, the nature of the contaminants that may dissolve into the reactive chemical process fluid, and the nature of the reactive chemical process fluid to be rinsed. Factors such as should be taken into account. Such a proposed rinsing fluid should also be compatible (i.e. relatively non-reactive) with the materials of construction with which it contacts. Rinsing fluids that can be used include, for example, water, organic solvents, mixtures of organic solvents, ozone-containing water, or combinations thereof. Suitable organic solvents include organic compounds useful in the drying solutions disclosed herein below, such as C ₁ to C ₁₀ alcohols, preferably C ₁ to C ₆ alcohols. Be done. This rinsing fluid is preferably liquid,
Deionized water is more preferred.

It is also possible for the rinsing fluid to additionally contain low levels of rinsing-enhancing chemically-reactive agents. For example, the rinsing fluid may be, for example, a dilute aqueous solution of hydrochloric acid or acetic acid that prevents metal deposits from adhering to the surface of the electronic component. Surfactants, anticorrosives and / or ozone are other additives used in rinsing fluids. The concentration of such additives in such rinsing fluids is low. This concentration is, for example, preferably about 100, based on the total weight of the rinsing fluid.
It is 0 ppm (weight) or less, and more preferably 100 ppm (weight) or less. In the case of ozone, the concentration of ozone added to the rinsing fluid is preferably 5 ppm or less.

Those skilled in the art will appreciate that the choice of reactive chemical process fluids, the order of reactive chemical process fluids and rinsing fluids, and processing conditions (eg, process fluid temperature, concentration, contact time and flow rate) are desired. It will be appreciated that it will depend on the wet processing results. For example, the electronic component may be contacted with the rinsing fluid before or after performing one or more chemical treatment steps. Alternatively, in some wet processing methods, one chemical treatment step is performed immediately followed by another chemical treatment step [the electronic components are not contacted with the rinsing fluid during the two chemical treatment steps ( That is, there is a possibility that it is preferable that no rinsing is involved). Such a sequential wet process without intervention of rinsing is, for example, US Application Serial No. 08 / 684,543 (filed Jul. 19, 1996).
This is incorporated herein by reference in its entirety).

In a preferred aspect of the present invention, the purpose is to contact the electronic component with the ozone-containing process fluid and then to aid in the removal of reaction byproducts or residual chemicals, such as oxidized organic materials. Then, the electronic component is contacted with at least one processing fluid (i.e., processing solution) that is a liquid. In particular, when attempting to remove organic materials from the surface of an electronic component using the ozone-containing process fluid, it is preferred to contact the electronic component afterwards. Such processing solutions may be reactive chemical process liquids or rinses or combinations thereof.

In one aspect of the invention, for example, the electronic component is contacted with an ozone-containing process fluid followed by a cleaning solution, such as an SC1 solution and / or an SC2 solution. After contacting the electronic component with the SC1 and / or SC2 solution, it may optionally be rinsed with a rinsing solution such as deionized water. The temperature of the SC1 solution is preferably about 15 ° C to about 95 ° C, more preferably about 25 ° C to about 45 ° C. The temperature of the SC2 solution is preferably about 15 ° C to about 95 ° C, more preferably about 25 ° C to about 45 ° C. The temperature of the rinse solution is preferably about 15 ° C to about 90 ° C, more preferably about 25 ° C to about 30 ° C.

In another aspect of the invention, the electronic component may be contacted with the ozone-containing process fluid prior to contacting with the etching solution. When the etching solution contains hydrofluoric acid, the temperature of the hydrofluoric acid is preferably about 15 ° C to about 95 ° C, more preferably about 35 ° C to about 40 ° C. The electronic components after this etching may be contacted with a rinsing solution, such as deionized water.
The temperature of the rinse is preferably about 15 ° C to 90 ° C, more preferably about 25 ° C to about 30 ° C.

In another aspect of the invention, after contacting the electronic component with an ozone-containing process fluid, the concentration of H ₂ O: H ₂ O ₂ : NH ₄ OH is about 80: 3: 1 by volume. SC1 solution, SC2 solution with an H ₂ O: H ₂ O ₂ : HCl concentration of 80: 1: 1 by volume, and H ₂ O: HF concentration of about 4: 1 to about 1000: 1 by volume fluorination. It may be brought into contact with a hydrogen acid solution. The method is particularly useful for cleaning and etching. The order of performing the treatment using the SC1 solution, the treatment using the SC2 solution and the treatment using the etching solution may be reversed. In a preferred aspect of the present invention, the electronic component is the ozone. Contact with the contained process fluid followed by contact with the SC1 solution and then with the SC2 solution. The electronic component is then preferably rinsed with deionized water and then dried with vapors of isopropanol.

Accordingly, there are a wide variety of methods that make it possible to subject electronic components to wet processing according to the method of the present invention. For the purpose of improving the degree of cleaning, it is also possible to carry out the wet treatment, for example using sonic energy (for example in the megasonic energy range) while the electronic component is in contact with the process fluid.
Such methods also include, for example, US Pat. No. 5,383,484, 1996.
US patent application serial number 08 / 684,543, 19 filed July 19, 2013
09/209, 101, filed December 10, 1998, and 1999, 2
09 / 253,157 filed on March 19, and provisional US patent application serial number 60 / 087,758 filed June 2, 1998 and 60/111 filed December 8, 1998. , 350 (the disclosures of which are incorporated herein by reference in their entireties).

The method of the present invention may generally be carried out in any wet processing equipment, such equipment including, for example, multiple baths (eg, wet bench) and single bath equipment (environmentally dependent). Can be open or closed). For example, Chapter 1 Over
view and Evolution of Semiconductor
Wafer Contamination and Cleaning Tec
Henology Werner Kern, and Chapter 3: Aqueous C
leaning Processes, Don C. Burkman, Dona
ld Deal, Donald C.I. Grant, and Charlie A .;
Peterson, Handbook of Semiconductor
Wafer Cleaning Technology [Werner Ker
Edited by Nyes Publication Parkridge (New Jersey) (1993)], and Wet Etch Clean
ing Hiroyuki Horiki and Takao Nakaza
w a, Ultraclean Technology Handbook 1
Vol., [Edited by Tadahiro Ohmi and published by Marcel Dekker] (the disclosures of which are incorporated herein by reference in their entirety).
checking ...

Suitably such wet processing equipment also includes storage tanks for chemical reactants such as ammonium hydroxide (NH ₄ OH) or hydrofluoric acid (HF), and rinsing and chemical reaction of electronic components. Also included is a device for delivering deionized water for use in body dilution. Such chemical reactants are preferably stored in concentrated form, ie hydrogen peroxide (H ₂ O ₂ ) (31%), NH ₄ OH (28%), hydrochloric acid (HCl) (37%), HF (
49%) and sulfuric acid (H ₂ SO ₄ ) (98%) (percentages represent weight percentages in aqueous solution). Such storage tanks are preferably assembled so that they are in fluid communication with the reaction chamber, in which the electronic components are processed.

Gaseous ozone is preferably generated outside the wet process reaction chamber. Ozone may be generated using any method known to those skilled in the art without departing from the spirit of the invention. Suitably, ozone is generated using a high capacity generator, such as TEX 8200, which is capable of producing ozone at a rate of approximately 100 grams / hour or higher.

In a preferred aspect of the invention, the electronic components are contained within a single tank device. Preferably,
U.S. Pat. No. 4,778,532,4,917,123,4,911,761,4,79
5,497,4,899,767,4,984,597,4,633,893,4,91
7,123,4,738,272,4,577,650,5,571,337 and 5,
569,330 (the disclosures of which are incorporated herein by reference in their entirety) using a single vessel apparatus. A suitable commercially available single tank device is a Full-Flow (such as that manufactured by CFM Technologies.
(Trademark) tank, Poseidon manufactured by Steag, and Dainipp
FL820L manufactured by on Screen. They are preferred because they allow easier control of foreign gas and pollution levels with such devices.

Suitably, such single bath wet processing equipment also includes metering equipment, such as control valves and pumps, for transporting the chemical reactants from the storage tank area to the reaction chamber. A processing controller, such as a personal computer, is typically used as a means for monitoring the processing conditions (for example, flow rate, maximum speed, contact time and temperature). For example, such a controller can be used to program the flow rates of chemical reactants and deionized water such that one or more chemical reactants are present in suitable amounts in the reactive chemical process fluid. it can.

In the most preferred embodiment of the invention, the electronic components are wet processed in a sealable single bath wet processing apparatus. Preferably, the sealable single bath wet process equipment is also capable of receiving different process fluids in different orders. The preferred method of delivering process fluid to the bath is to directly replace one fluid with another. Full-F manufactured by CFM Technologies, Inc.
The Low ™ wet processing system is an example of a system that has the ability to transport fluids in direct displacement. Such devices are preferred because they result in more uniform processing of the electronic components. In addition, the chemicals used in the chemical processing of electronic components are often extremely dangerous in that they can be strong acids, alkalis or volatile solvents. Use of such process fluids because the use of a single tank that can be sealed avoids atmospheric contamination, avoids human contact with chemicals and allows for safer handling of chemicals. The risks associated with this are minimized.

In a preferred method of the present invention using a single, sealed vessel, one or more electronic components are placed in a single vessel and sealed to the environment. The electronic components may optionally be contacted with one or more process fluids for pretreatment. The surface of the electronic component is wetted by contacting the electronic component after it has undergone any desired pretreatment steps with a wetting solution, such as a basic solution. Such contacting can be accomplished by pumping the wetting solution into the bath and filling the process bath with the wetting solution, so that gas from the atmosphere also precedes the previous step. The residual fluid derived is also not significantly captured in the vessel. The fluid may be continuously directed into the bath after the bath is filled with the wetting solution, or the flow of the wetting solution may be stopped to allow the electronic components to soak for the desired time. It is also possible.
The electronic component is then contacted with the ozone-containing process fluid by introducing the ozone-containing process fluid into the tank after removing the wetting solution from the tank. Suitably, a base is present in the bath during at least a portion of the time that the electronic component is contacted with the ozone containing process fluid. After contacting the electronic component with the ozone-containing process fluid, it may optionally be rinsed with a rinsing fluid and / or contacted with another process fluid, such as one or more reactive chemical process fluids.

The transfer of replacing one process fluid in another single sealed vessel with another process fluid can be accomplished in several ways. For example, the process fluid contained in the process vessel may be completely removed (ie, drained), and the next process fluid may be pumped into the vessel during or after this draining. Alternatively, it is also possible to expel the process fluid present in the vessel directly with the next desired process fluid, for example as described in US Pat. No. 4,778,532.

The electronic components are preferably dried after being wet treated with a reactive chemical process fluid or a rinsing fluid. "Drying" or "drying" means preferably substantially removing the droplets from the electronic component. When the droplets are removed during the drying, the impurities existing in the droplet state do not remain on the surface of the semiconductor substrate when the droplets are evaporated. Such impurities undesirably leave marks (eg water marks) or other residues on the surface of the semiconductor substrate. However, also
It is also contemplated that the drying may involve simply removing the processing or rinsing fluid, for example using a drying fluid stream or other means known to those skilled in the art.

Any drying method and drying device can be used. Suitable drying methods include e.g. evaporation, centrifugal force in a spin-rinser-dryer, steam or chemical drying,
Or the combination etc. are included. In a preferred embodiment, wet processing and drying are carried out in the bath without removing the electronic components from a single bath.

A preferred drying method uses a drying fluid stream for the purpose of directly displacing the last processing solution that was in contact with the electronic components before drying (hereinafter referred to as “direct eviction drying”). Suitable methods and apparatus for direct drive-off drying are described, for example, in U.S. Pat. No. 4,778,532,4,795,497,4,911,761,4,984,597.
, 5,571,337 and 5,569,330. Other direct expulsion dryers that can be used include Steag, Dainippon and Yiel.
Included are manufacturer-supplied Marangoni type dryers such as dUp.

The drying fluid stream is preferably produced from a partially or completely evaporated drying solution. The drying fluid stream may be, for example, superheated steam, a mixture of steam and gas, saturated steam, or a mixture of steam and non-condensable gas.

The drying solution selected for the purpose of producing such a drying fluid stream is preferably a solution that is miscible with the process fluid last placed in the bath and does not react with the surface of the electronic component. . Preferably, the boiling point of such a drying solution is also relatively low so that the drying can be carried out easily. Such a drying solution is preferably selected from organic compounds having a boiling point below about 140 ° C., for example at atmospheric pressure. Examples of drying solutions which can be used are steam, alcohols such as methanol, ethanol, 1-propanol, isopropanol, n-butanol, s-butanol,
Acetone, acetonitrile, hexafluoroacetone, nitromethane, acetic acid, propionic acid, monomethyl ether of ethylene glycol, difluoroethane, ethyl acetate, isopropyl acetate, 1,1,2-trichloro-1, etc., such as t-butanol or t-amyl alcohol. 2,2-trifluoroethane, 1,2-dichloroethane, trichloroethane, perfluoro-2-butyltetrahydrofuran, perfluoro-1,4-dimethylcyclohexane or a combination thereof. Preferably, such a drying solution is a C ₁ to C ₆ alcohol such as methanol, ethanol, 1-propanol, isopropanol, n-butanol,
It is s-butanol, t-butanol, t-amyl alcohol, pentanol, hexanol or a combination thereof.

In a preferred embodiment of the present invention, a drying solution is selected which is mixed with the processing solution existing in the process tank immediately before drying to form a minimum boiling point azeotrope together with the processing solution. Drying solutions that form a minimum boiling azeotrope with water are especially preferred because water is the most convenient and commonly used solvent in chemical processing or rinsing fluids.

The dried electronic component may be removed from the drying bath and subjected to further treatment in any desired manner.

Although the present invention has been described above in terms of particular preferred embodiments, it will be apparent to those skilled in the art that numerous modifications and variations can be made to such matters. The statements made above are for purposes of illustration and are not intended to limit the invention.

[Procedure for Amendment] Submission for translation of Article 34 Amendment of Patent Cooperation Treaty

[Submission date] September 7, 2000 (200.9.7)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Claims

[Correction method] Change

[Contents of correction]

[Claims]

─────────────────────────────────────────────────── ─── Continued front page    (81) Designated countries EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, I T, LU, MC, NL, PT, SE), OA (BF, BJ , CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, K E, LS, MW, SD, SL, SZ, UG, ZW), E A (AM, AZ, BY, KG, KZ, MD, RU, TJ , TM), AE, AL, AM, AT, AU, AZ, BA , BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GD, G E, GH, GM, HR, HU, ID, IL, IN, IS , JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, M N, MW, MX, NO, NZ, PL, PT, RO, RU , SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, UZ, VN, YU, ZA, Z W F-term (reference) 2H096 AA25 LA03                 4G075 AA24 AA30 AA62 BA06 BC06                       BC10 BD16 BD26 CA02 CA51                 5F043 AA01 BB27 GG10                 5F046 MA02 MA05

Claims (28)

[Claims] 1. A method of wet processing an electronic component, comprising: (a) contacting the surface of the electronic component with a wetting solution containing water to bring the surface of the electronic component to the wetting solution. And (b) producing an ozone-containing process fluid in the form of a gas, vapor, mist or mixture thereof comprising gaseous ozone, and (c) bringing said electronic component into said reaction chamber containing said ozone. The process fluid is contacted for a contact time, but at least one base is present during at least a portion of the contact time, and the temperature of the ozone-containing process fluid is about 20 ° C to about 145 ° C.
At a temperature of about 100 ° C. and the base is present in the wetting solution or in the ozone-containing process fluid or a combination thereof. 2. The method of claim 1, further comprising contacting the electronic component with the ozone-containing process fluid prior to contacting the electronic component with at least one processing solution. 3. The base is selected from the group consisting of ammonia, ammonium hydroxide, alkylammonium hydroxide, alkali metal hydroxides, alkaline earth metal hydroxides, organic amines, basic amino acids and combinations thereof. The method of claim 1, wherein 4. The method of claim 3, wherein the base is present in the wetting solution. 5. The method of claim 4 wherein the base is selected from the group consisting of ammonium hydroxide, alkyl ammonium hydroxide, alkali metal hydroxides, alkaline earth metal hydroxides, and combinations thereof. 6. The base is present in the ozone-containing process fluid, is in the form of a vapor, a gas or a combination thereof and is selected from the group consisting of ammonia, alkylammonium hydroxide, organic amines and combinations thereof. Item 3. The method according to Item 3. 7. The method of claim 1, wherein the ozone-containing process fluid further comprises a hydroxide fluid comprising water, hydrogen peroxide, a base or a combination thereof. 8. The method of claim 7 wherein said gaseous ozone and said hydroxide fluid are combined in said reaction chamber to produce said ozone containing process fluid. 9. The method of claim 8, wherein the hydroxide fluid is ammonia, a fog of water, steam or a combination thereof. 10. Ozone and water are combined to produce ozone-containing water and the ozone-containing water is blown with a carrier gas to produce an ozone-containing process fluid comprising water vapor, ozone and the carrier gas. The method of claim 1, wherein an ozone containing process fluid is produced. 11. A method for wet processing of electronic components, comprising: (a) filling a large number of electronic components in a single sealable vessel, (b) including water on the surface of the electronic components. An ozone-containing process fluid in the form of a gas, vapor, mist or mixture thereof comprising (c) gaseous ozone, by contacting the wetting solution with the surface of the electronic component with the wetting solution. And (d) contacting the electronic component in the reaction chamber with the ozone-containing process fluid for a contact time, wherein at least one base is present during at least a portion of the contact time, and the ozone is The temperature of the contained process fluid is from about 20 ° C to about 145 ° C
At a temperature of about 100 ° C. and the base is present in the wetting solution or in the ozone containing process fluid or a combination thereof, and (e) contacting the electronic component with the ozone containing process fluid. And then contacting the electronic component with one or more processing solutions in the bath. 12. The base is selected from the group consisting of ammonia, ammonium hydroxide, alkyl ammonium hydroxide, alkali metal hydroxides, alkaline earth metal hydroxides, organic amines, basic amino acids and combinations thereof. The method according to claim 11, wherein 13. The method of claim 12, wherein the base is present in the wetting solution. 14. The method of claim 13 wherein the base is selected from the group consisting of ammonium hydroxide, alkyl ammonium hydroxide, alkali metal hydroxides, alkaline earth metal hydroxides, and combinations thereof. 15. The base is present in the ozone-containing process fluid, is in the form of a vapor, a gas or a combination thereof and is selected from the group consisting of ammonia, alkyl ammonium hydroxides, organic amines and combinations thereof. Item 12. The method according to Item 12. 16. The ozone-containing process fluid further comprising water, hydrogen peroxide,
12. The method of claim 11, which also includes a hydroxide fluid comprising a base or a combination thereof. 17. The method of claim 16 wherein said gaseous ozone and said hydroxide fluid are combined in said vessel to produce said ozone containing process fluid. 18. The method of claim 17, wherein the hydroxide fluid is ammonia, a fog of water, steam or a combination thereof. 19. The method of claim 18, wherein the hydroxide fluid is ammonia. 20. The ozone-containing process of contacting the electronic component with the wetting solution by filling the bath with the wetting solution and during or after removing the wetting solution from the bath. The method of claim 11, wherein the electronic component is contacted with the ozone-containing process fluid by directing a fluid into the bath. 21. The method of claim 11, wherein at least one of the treating solutions comprises water, hydrogen peroxide and ammonium hydroxide. 22. The method of claim 21, wherein the electronic component is dried in the bath. 23. A method of wet processing an electronic component comprising: (a) contacting the electronic component with a wetting solution comprising water and at least one base to render the surface of the electronic component Moistening with a wetting solution, (b) contacting the moistened electronic component with an ozone-containing process fluid for a contact time, the ozone-containing process fluid being in the form of a gas, a vapor, a mist or a mixture thereof, and Bringing the ozone-containing process fluid to a temperature of about 20 ° C. to about 145 ° C., and (c) setting the electronic component to 1 after contacting the electronic component with gaseous ozone.
Contacting with one or more processing fluids. 24. The method of claim 23, wherein the ozone-containing process fluid is gaseous ozone or a mixture comprising gaseous ozone and at least one hydroxide fluid. 25. The base in the wetting solution is ammonium hydroxide, alkylammonium hydroxide, alkali metal hydroxide, alkaline earth metal hydroxide,
24. The method of claim 23, selected from the group consisting of organic amines, basic amino acids and combinations thereof. 26. The method of claim 25, wherein the ozone-containing process fluid further comprises a second base. 27. The method of claim 26, wherein the second base is ammonia. 28. The ozone-containing process of contacting the electronic component with the wetting solution by filling the bath with the wetting solution and during or after removing the wetting solution from the bath. 24. The method of claim 23, wherein the electronic component is contacted with the ozone-containing process fluid by directing a fluid into the bath.