KR102616035B1 - Method of forming patterned thin film and method of manufacturing device using the same - Google Patents

Abstract

A method of forming a patterned thin film and a method of manufacturing a device using the same are disclosed. The disclosed thin film forming method includes forming a sublimable material layer on a partial area of a substrate and using the sublimable material layer as a mask layer to form a thin film on an area of the substrate in which the sublimable material layer is not formed. May include steps. The thin film may have a shape defined by the sublimable material layer. At least a portion of the sublimable material layer may be sublimated while forming the thin film.

Description

Method of forming a patterned thin film and method of manufacturing a device using the same {Method of forming patterned thin film and method of manufacturing device using the same}

The present invention relates to a method of forming a thin film by vapor deposition and its application, and more specifically, to a method of forming a thin film with a pattern having a predetermined shape and a method of manufacturing a device using the same.

When manufacturing various electronic devices, including semiconductor devices, various thin films made of semiconductors, insulators, or conductors (e.g., metals) are formed on a substrate. Various methods are applied to form thin films, such as physical vapor deposition (PVD), chemical vapor deposition (CVD), and atomic layer deposition (ALD). Additionally, various patterning technologies are being used to form thin films patterned into the shapes required for devices.

Deposition means attaching a material to the surface of a substrate as a thin film using a vapor phase precursor. For example, deposition by evaporation means heating and evaporating a metal or compound in a vacuum and coating the vapor as a thin film on the surface of the object. During the manufacturing process of organic light emitting devices (OLEDs), there are roughly four vacuum deposition methods, which are a field of pixel formation technology. Among these, the method applied to mass production is metal mask (hereinafter, metal mask). It is a vacuum deposition method using (referred to as MM).

Because organic materials for OLED are highly reactive and vulnerable to water and oxygen, the organic material deposition process must be carried out in an environment blocked from water and oxygen. In other words, it may not be possible to use a general photolithography process. The vacuum deposition method using MM is a method in which the MM is placed close to the substrate between the evaporation source and the substrate in a vacuum chamber, and then the organic material evaporated from the evaporation source is passed through the MM and deposited on the substrate. The vacuum deposition method using MM has been technically verified, and the development of materials and equipment is also showing considerable maturity.

However, since the vacuum deposition method using MM has fatal problems in realizing large-area high resolution, it has the disadvantage that it is inherently difficult to reduce production costs due to the use of expensive equipment. MM is made using a metal such as INVAR (FeNi36), which has the minimum thermal expansion coefficient, and is manufactured in the form of a very elaborate aperture-type pixel pattern of several tens of ㎛ on a thin metal film of about 15 to 30 ㎛ to realize the pixel size. do. In order to produce a high-resolution display screen, the pixel size and the gap between pixels must be reduced, but MM is limited in reducing the pixel size due to the minimum required thickness. In addition, since deposition is performed using an evaporation source, the substrate and MM are placed on the upper side of the evaporation source (source), and if the substrate and mask are thin and have a large area, the problem of their sagging occurs. Sagging of the substrate and mask increases as the size of the substrate increases, which may cause defects such as scratches or problems in which pixels are not accurately implemented.

In addition, when depositing a thin film using MM, the thickness of the deposited thin film is about tens to hundreds of nm, which is significantly lower than the thickness of MM, so there are many limitations in implementing accurate shapes and fine pixels due to the shadowing effect caused by MM. . In other words, because the thickness of the OLED composition thin film is very thin compared to the MM thickness, a shadowing effect occurs and it is difficult to implement fine and precise patterns.

Therefore, a new thin film formation method that can overcome various problems and limitations of the existing thin film formation method using MM is required.

The technical problem to be achieved by the present invention is to provide a thin film formation method that can form a patterned material film or thin film in a new way without a metal mask such as a conventional MM (metal mask) when implementing the pixels of a device.

In addition, the technical problem to be achieved by the present invention is to provide a method of manufacturing an electronic device, for example, an organic light-emitting device, using the thin film formation method described above.

The problem to be solved by the present invention is not limited to the problems mentioned above, and other problems not mentioned will be understood by those skilled in the art from the description below.

According to one embodiment of the present invention, a method of forming a patterned thin film includes forming a sublimable material layer on a partial region of a substrate; and forming a thin film on an area of the substrate where the sublimable material layer is not formed using the sublimable material layer as a mask layer, wherein the thin film has a shape defined by the sublimable material layer. A method of forming a thin film is provided, wherein at least a portion of the sublimable material layer is sublimated while forming the thin film.

The sublimable material layer may include a material having a melting point in the range of 60°C to 210°C at 1 atm.

The sublimable material layer is made of naphthalene, anthracene, methyl substituents of anthracene (e.g., 9-methylanthracene, 2-methylanthracene, 9,10-dimethylanthracene), phenanthrene, and phenanthrene. It may contain at least one methyl substituent (eg, 3-methylphenanthrene).

The sublimable material layer may be formed to have a thickness of about 1 nm to 10 μm.

The sublimable material layer can be formed using a PVD method, a printing method based on a solution process, or an application method based on a solution process.

The thin film may include an organic material.

The thin film may include an organic light-emitting material.

The thin film can be formed using a PVD method.

When forming the thin film, the temperature of the substrate can be adjusted to about 10 to 90 °C.

The entire sublimable material layer can be removed by sublimation.

According to another embodiment of the present invention, forming a thin film on a substrate using the above-described thin film forming method; and manufacturing an electronic device including the thin film.

According to another embodiment of the present invention, there is a method of manufacturing an organic light emitting device having a plurality of pixel portions, comprising forming a first sublimable material layer having a plurality of first opening regions corresponding to a plurality of first pixel regions on a substrate. steps; and forming a patterned first organic material layer in the plurality of first pixel regions of the substrate using the first sublimable material layer as a first mask layer, wherein the patterned first organic material layer A method of manufacturing an organic light emitting device wherein the material layer has a shape defined by the first sublimable material layer, and at least a portion of the first sublimable material layer is sublimated while forming the patterned first organic material layer. This is provided.

The first sublimable material layer is made of naphthalene, anthracene, methyl substituents of anthracene (e.g., 9-methylanthracene, 2-methylanthracene, 9,10-dimethylanthracene), phenanthrene, and phenene. It may contain at least one of the methyl substituents of tren (e.g., 3-methylphenanthrene).

The first sublimable material layer may be formed to have a thickness of about 1 nm to 10 μm.

The patterned first organic material layer may be a first organic light-emitting layer.

When forming the patterned first organic material layer, the temperature of the substrate may be adjusted to about 10 to 90 °C.

The entire first layer of sublimable material can be removed by sublimation.

After forming the patterned first organic material layer, covering the patterned first organic material layer on the substrate, having a plurality of second opening regions corresponding to a plurality of second pixel regions. forming a second layer of sublimable material; and forming a patterned second organic material layer in the plurality of second pixel regions of the substrate using the second sublimable material layer as a second mask layer.

The patterned second organic material layer may be a second organic light-emitting layer.

After forming the patterned second layer of organic material, a plurality of third openings corresponding to a plurality of third pixel regions are formed covering the first and second patterned organic material layers on the substrate. forming a third layer of sublimable material having regions; and forming a patterned third organic material layer in the plurality of third pixel regions of the substrate using the third sublimable material layer as a third mask layer.

The patterned third organic material layer may be a third organic light-emitting layer.

According to embodiments of the present invention, it is possible to implement a thin film formation method that can form a patterned material film (thin film) in a new way without using an existing metal mask when implementing pixels of a device. By using the thin film formation method according to the embodiment, various problems and limitations of the existing thin film formation method using MM, such as sagging and cleaning of the MM and shadowing effect when implementing pixels, can be overcome.

Additionally, according to embodiments of the present invention, various electronic devices can be easily manufactured using the thin film forming method described above. In particular, using the thin film formation method described above, a patterned organic light emitting device with excellent performance and high resolution can be more easily manufactured.

1A to 1C are cross-sectional views illustrating a thin film forming method according to an embodiment of the present invention.
FIG. 2 is a cross-sectional view exemplarily showing the configuration of deposition equipment that can be used in the step of FIG. 1B.
3A to 3J are plan views illustrating a method of manufacturing an organic light emitting device (OLED) by applying a thin film forming method according to an embodiment of the present invention.
4A to 4E are cross-sectional views illustrating a method of manufacturing an organic light emitting device (OLED) by applying a thin film forming method according to an embodiment of the present invention.
5 and 6 are photographic images showing a case in which a sublimable material layer is formed on a glass substrate according to an exemplary embodiment of the present invention.
Figure 7 shows an exemplary embodiment of the present invention, in which a sublimable material layer is formed on a glass substrate and then a patterned thin film is formed on the glass substrate using the sublimable material layer as a mask. This is a photographic image showing.

Hereinafter, embodiments of the present invention will be described in detail with reference to the attached drawings.

The embodiments of the present invention described below are provided to explain the present invention more clearly to those skilled in the art, and the scope of the present invention is not limited by the examples below. The embodiment may be modified in several different forms.

The terms used herein are used to describe specific embodiments and are not intended to limit the invention. As used herein, singular terms may include plural forms unless the context clearly indicates otherwise. Additionally, as used herein, the terms “comprise” and/or “comprising” refer to the term “comprise” and/or “comprising” to specify the presence of the mentioned shapes, steps, numbers, operations, members, elements and/or groups thereof. and does not exclude the presence or addition of one or more other shapes, steps, numbers, operations, members, elements and/or groups thereof. In addition, the term "connection" used in this specification not only means that certain members are directly connected, but also includes indirectly connected members with other members interposed between them.

In addition, when a member is said to be located “on” another member in the present specification, this includes not only the case where a member is in contact with another member, but also the case where another member exists between the two members. As used herein, the term “and/or” includes any one and all combinations of one or more of the listed items. In addition, terms such as “about” and “substantially” used in the specification herein are used in the sense of a range or close to the numerical value or degree, taking into account unique manufacturing and material tolerances, and to aid understanding of the present application. Precise or absolute figures provided for this purpose are used to prevent infringers from taking unfair advantage of the stated disclosure.

Hereinafter, embodiments of the present invention will be described in detail with reference to the attached drawings. The size or thickness of areas or parts shown in the attached drawings may be somewhat exaggerated for clarity of specification and convenience of explanation. Like reference numerals refer to like elements throughout the detailed description.

1A to 1C are cross-sectional views illustrating a thin film forming method according to an embodiment of the present invention.

Referring to FIG. 1A, a sublimable material layer 20 may be formed on a partial area of the substrate 10. The sublimable material layer 20 may be formed to cover the partial area of the substrate 10, and other partial areas of the substrate 10 may be exposed without being covered by the sublimable material layer 20. It may be said that the sublimable material layer 20 is formed on the first region of the upper surface of the substrate 10, and the sublimable material layer 20 may not be formed on the second region of the upper surface of the substrate 10.

The sublimable material layer 20 is a material whose triple point is higher than the process pressure and temperature for forming a thin film, and may include a material that can change phase directly from the solid phase to the gas phase without passing through the liquid phase during the process. You can. These materials may have a lower melting point than the gaseous precursor for thin film formation at the process temperature. Under process conditions for forming an organic thin film, the sublimable material layer 20 may include an aromatic hydrocarbon compound having excellent sublimation properties under process conditions for forming a thin film.

In one embodiment, the aromatic hydrocarbon compound is naphthalene, anthracene, 9-Methylanthracene, 2-Methylanthracene, 9,10- It may include dimethylanthracene (9,10-Dimethylanthracene), phenanthrene, and 3-methylphenanthrene. These examples are illustrative and may also include other isomers of naphthalene or anthracene and mixtures of two or more of them.

These sublimable materials may include materials with a melting point in the range of 60°C to 210°C at 1 atm. If the melting point exceeds 210°C, the sublimation property may not be sufficient, and a deposition target material film, which will be described later, may be formed on the sublimable material layer 20. If the melting point is less than 60°C, the organic thin film may be melted during the formation of the organic thin film. There is a problem that the thin film invades the pixel pattern to be formed, preventing the deposition target material film from being clearly defined, or disappears before the formation of the deposition target material film is completed.

For example, the sublimable material layer 20 may be formed to have a thickness of about 1 nm to 10 μm. When this thickness range is satisfied, the thin film formation process using the sublimable material layer 20 can proceed more easily. If the thickness of the sublimable material layer 20 is too thin, about 1 nm or less, the sublimable material layer 20 may be removed too quickly and may not fully perform its role as a mask. Additionally, if the thickness of the sublimable material layer 20 is too thick, such as about 10 ㎛ or more, the efficiency of the process may be reduced because a long time is required to remove the sublimable material layer 20. Accordingly, the sublimable material layer 20 may preferably have a thickness of about 1 nm to 10 μm. However, depending on various process conditions, the appropriate thickness or usable thickness range of the sublimable material layer 20 may vary.

The sublimable material layer 20 can be formed using, for example, a physical vapor deposition (PVD) method, a printing method based on a solution process, or a coating method based on a solution process. Here, the PVD method may be, for example, an evaporation method. At this time, the sublimable material layer 20 may be formed by a method different from the existing vacuum deposition method using a fine metal mask (MM). For example, with the substrate 10 disposed below and the supply portion of the source material disposed above the substrate 10, the evaporated source material (i.e., the source material of the sublimable material) is supplied to the substrate ( By supplying to the upper surface of 10), the sublimable material layer 20 can be formed. At this time, a predetermined mask member may be disposed on the substrate 10, and the shape of the sublimable material layer 20 may be limited by the mask member. This method of forming the sublimable material layer 20 may be completely different from the existing vacuum deposition method using MM, that is, the existing method of performing deposition with the MM and substrate placed above the evaporation source (source).

Additionally, the sublimable material layer 20 may be formed using a printing method based on a solution process or an application method based on a solution process. At this time, the sublimable material can be mixed with a predetermined solvent to form a solution containing the sublimable material, and the sublimable material layer 20 can be formed by printing or applying the solution on the substrate 10. there is. In this case, the sublimable material layer 20 may contain residual solvent. The solvent may be a volatile solvent such as alcohol or benzene. However, depending on the case, the type of solvent may vary. Depending on the material of the upper surface of the substrate 10, the type of solvent that can be used may also vary.

Referring to FIG. 1B, the thin film 30 can be formed on an area of the substrate 10 where the sublimable material layer 20 is not formed by using the sublimable material layer 20 as a mask layer. Accordingly, the thin film 30 may have a shape defined by the sublimable material layer 20. The thin film 30 may be a ‘deposition target material film’ to be formed through the process of this embodiment. The thin film 30 may also be referred to as a ‘material layer’ or a ‘film’. The thin film 30 may have a thickness range that various material films used in general electronic devices or semiconductor devices can have. For example, the thickness of the thin film 30 may be about 1 nm to 10 μm, but this is an example and the thickness range of the thin film 30 may vary.

The thin film 30 can be formed using, for example, a PVD method. The PVD method may be, for example, an evaporation method. At this time, the thin film 30 may be formed using a method different from the existing vacuum deposition method using MM. For example, with the substrate 10 disposed below and the source material supply unit disposed above the substrate 10, the evaporated source material (i.e., source material for deposition of the thin film 30) is supplied. The thin film 30 can be formed by supplying it to the upper surface of the substrate 10 through the part. At this time, the sublimable material layer 20 provided on the substrate 10 may serve as a mask layer, and the shape/pattern of the thin film 30 may be limited by the sublimable material layer 20. This method of forming the thin film 30 may be completely different from the existing vacuum deposition method using MM, that is, the existing method of performing deposition with the MM and substrate placed above the evaporation source (source).

While forming the thin film 30, at least a portion of the sublimable material layer 20 may be sublimated. As vapor is generated from the upper surface of the sublimable material layer 20, the source material for depositing the thin film 30 may not be deposited on the sublimable material layer 20. In addition, even if the source material for deposition of the thin film 30 is partially attached to the sublimable material layer 20, the attached source material may be desorbed and removed during the sublimation process of the sublimable material layer 20. Accordingly, the thin film may not be deposited on the sublimable material layer 20, and the thin film 30 may be selectively deposited only on portions of the substrate 10 where the sublimable material layer 20 is not formed.

When forming the thin film 30, the temperature of the substrate 10 may be adjusted to about 10 to 90 °C or about 10 to 50 °C. In this case, deposition of the thin film 30 can be performed more easily, and sublimation of the sublimable material layer 20 can also proceed easily. By controlling the temperature of the substrate 10, the deposition rate of the thin film 30 and the sublimation rate of the sublimable material layer 20 can be controlled. In some cases, the temperature of the substrate 10 may change over time. Additionally, in some cases, the temperature of the substrate 10 may be maintained at room temperature.

The thin film 30 may include, for example, an organic material. In other words, the thin film 30 may be an organic material film or a film containing an organic material. As a specific example, the thin film 30 may include an organic light-emitting material applied to an organic light-emitting device (OLED). In this case, the thin film 30 may be an ‘organic light emitting layer’. As the organic light emitting material of the thin film 30, any organic light emitting material used in general organic light emitting devices (OLEDs) can be used. Using the method according to the embodiment of the present invention, the organic light-emitting layer of an organic light-emitting device (OLED) can be formed in a completely different way than before.

According to an embodiment of the present invention, the entire sublimable material layer 20 can be removed by sublimation. FIG. 1C shows a state in which the entire sublimable material layer 20 in FIG. 1B has been sublimated and removed. As shown in FIG. 1C, a thin film 30 defined (patterned) in a predetermined shape may be formed on the substrate 10.

FIG. 2 is a cross-sectional view exemplarily showing the configuration of deposition equipment that can be used in the step of FIG. 1B.

Referring to FIG. 2, deposition equipment that can be used in the step of depositing the thin film 30 of FIG. 1b described above may include a supply unit 50 of a source material for depositing the thin film 30. The supply unit 50 may be referred to as a 'vapor injector', a 'vapor providing head', or a 'shower head'. The supply unit 50 may be disposed above the substrate 10 . The evaporated source material may be supplied to the upper surface of the substrate 10 through the supply unit 50. At this time, a predetermined carrier gas may be used to supply the source material. The carrier gas may be an inert gas such as N ₂ gas or Ar gas. The thin film 30 can be formed by supplying the evaporated source material to the upper surface of the substrate 10 through the supply unit 50. This method of forming the thin film 30 may be completely different from the existing vacuum deposition method using MM, that is, the existing method of performing deposition with the MM and substrate placed above the evaporation source (source).

In additional explanation, the susceptor (not shown) on which the substrate 10 is placed in the deposition equipment may be maintained at a temperature of, for example, about 50° C. or lower. The temperature when the source material evaporates from the source container (not shown) and reaches the supply unit 50 may be about 300° C. or higher. Since the temperature of the substrate 10 may be quite low compared to the temperature when the source material evaporates and reaches the supply unit 50 at a high temperature of about 300° C. or higher, the gaseous source material is transferred from the supply unit 50 to the substrate ( 10), a temperature drop may occur. As a result, substrate deposition can be achieved by condensation of the source material on the surface of the substrate 10. However, if the temperature of the source material is lowered below the critical temperature before it reaches the surface of the substrate 10, the source material may be condensed in advance before reaching the substrate 10 and thin film formation may not occur properly. there is. In this regard, at the time the source material reaches the surface of the substrate 10, the temperature of the source material may preferably be in the range of about 180°C to 250°C. These temperature conditions may vary depending on the type of source material or other process conditions.

1A to 1C and FIG. 2 illustrate the case of depositing the thin film 30 by a PVD method such as an evaporation method, but the method of depositing the thin film 30 may vary in various ways. For example, thin film 30 may be deposited using any CVD method. Additionally, the thin film 30 may be a predetermined inorganic material film or an organic-inorganic mixed film rather than an organic material film.

The thin film formation method according to the embodiment described above can be applied to the manufacture of various electronic devices. After forming a thin film on a substrate using the method according to the above embodiment, an electronic device portion including the thin film is formed on the substrate, thereby manufacturing a desired electronic device. The types and structures of the electronic devices may vary. For example, an organic light emitting device (OLED) can be manufactured by applying the thin film formation method according to an embodiment of the present invention. Examples are shown in FIGS. 3A to 3J.

3A to 3J are plan views illustrating a method of manufacturing an organic light emitting device (OLED) by applying a thin film forming method according to an embodiment of the present invention.

Referring to FIG. 3A, a predetermined substrate portion 100 may be prepared. The substrate unit 100 may include a substrate for forming an organic light emitting device (OLED) and a predetermined lower structure provided on the upper surface of the substrate.

Referring to FIG. 3B, a first sublimable material layer 210 having a plurality of first opening regions H10 corresponding to a plurality of first pixel regions may be formed on the substrate 100. The material, thickness, formation method, etc. of the first sublimable material layer 210 may be the same as those described for the sublimable material layer 20 in FIG. 1A. Therefore, the first sublimable material layer 210 is made of naphthalene, anthracene, 9-Methylanthracene, 2-Methylanthracene, and 9,10-dimethylanthracene (9). , 10-Dimethylanthracene, phenanthrene, and 3-methylphenanthrene may contain at least one sublimable material. Additionally, the thickness of the first sublimable material layer 210 may be, for example, about 1 nm to 10 μm. Additionally, the characteristics of the first sublimable material layer 210 may be the same or similar to those of the sublimable material layer 20 of FIG. 1A.

Referring to FIG. 3C, a first sublimable material layer 210 is used as a first mask layer to form a first organic material layer 310 patterned in the plurality of first pixel regions of the substrate 100. can do. That is, the patterned first organic material layer 310 may be formed in the plurality of first opening regions H10 corresponding to the plurality of first pixel regions. The patterned first organic material layer 310 may have a shape defined by the opening pattern of the first sublimable material layer 210 . While forming the patterned first organic material layer 310, at least a portion or all of the first sublimable material layer 210 may be sublimated.

The patterned first organic material layer 310 may correspond to the thin film 30 of FIG. 1B, and the thickness, formation method, etc. of the patterned first organic material layer 310 correspond to the thin film 30 of FIG. 1B. It may be the same or similar as described for. When forming the patterned first organic material layer 310, the temperature of the substrate portion 100 may be adjusted to about 10 to 90 °C or about 10 to 50 °C. Additionally, process characteristics related to the formation of the patterned first organic material layer 310 may be the same or similar to those described for the thin film 30 in FIG. 1B.

The patterned first organic material layer 310 may be a first organic light-emitting layer. The first organic light-emitting layer may be any one of a red (R) light-emitting layer, a green (G) light-emitting layer, and a blue (B) light-emitting layer of an organic light-emitting device (OLED). For example, the first organic emission layer may be a red emission layer. In this case, any organic material used in the red light-emitting layer of a general organic light-emitting device (OLED) may be used as the material for the first organic light-emitting layer.

In one embodiment, the entire first sublimable material layer 210 may be removed by sublimation. FIG. 3D shows a state in which the entire first sublimable material layer 210 in FIG. 3C has been removed. As shown in FIG. 3D, a patterned first organic material layer 310 may be formed on the substrate 100.

Referring to FIG. 3E, a second sublimable material layer 220 may be formed on the substrate 100. The second sublimable material layer 220 may be formed to cover the patterned first organic material layer (310 in FIG. 3D). Additionally, the second sublimable material layer 220 may have a plurality of second opening areas H20 corresponding to a plurality of second pixel areas. The material, thickness, forming method, etc. of the second sublimable material layer 220 may be the same or similar to those described for the first sublimable material layer 210 in FIG. 3B. Accordingly, detailed description of the second sublimable material layer 220 will be omitted.

Referring to FIG. 3F, the second sublimable material layer 220 is used as a second mask layer to form a second organic material layer 320 patterned in the plurality of second pixel regions of the substrate 100. can do. That is, the patterned second organic material layer 320 may be formed in the plurality of second opening regions H20 corresponding to the plurality of second pixel regions. The patterned second organic material layer 320 may have a shape defined by the second sublimable material layer 220 . While forming the patterned second organic material layer 320, at least a portion of the second sublimable material layer 220 may be sublimated. The second patterned organic material layer 320 may correspond to the thin film 30 of FIG. 1B, and the thickness, formation method, etc. of the second patterned organic material layer 320 are similar to those of the thin film 30 of FIG. 3C. 1 It may be the same or similar to what was described for the organic material layer 310.

The patterned second organic material layer 320 may be a second organic light-emitting layer. The second organic light-emitting layer may be any one of a red (R) light-emitting layer, a green (G) light-emitting layer, and a blue (B) light-emitting layer of an organic light-emitting device (OLED). For example, the second organic light-emitting layer may be a green light-emitting layer. In this case, any organic material used in the green light-emitting layer of a general organic light-emitting device (OLED) may be used as the material for the second organic light-emitting layer.

The entire second sublimable material layer 220 may be removed by sublimation. Figure 3g shows a state in which the entire second sublimable material layer 220 in Figure 3f has been removed. As shown in FIG. 3G, a patterned second organic material layer 320 may be formed on the substrate 100. The second patterned organic material layer 320 may be disposed adjacent to the first patterned organic material layer 310.

Referring to FIG. 3H, a third sublimable material layer 230 may be formed on the substrate 100. The third sublimable material layer 230 may be formed to cover the patterned first organic material layer (310 in FIG. 3g) and the second organic material layer (320 in FIG. 3g). Additionally, the third sublimable material layer 230 may have a plurality of third opening areas H30 corresponding to a plurality of third pixel areas. The material, thickness, forming method, etc. of the third sublimable material layer 230 may be the same or similar to those described for the first sublimable material layer 210 in FIG. 3B.

Referring to FIG. 3I, a third sublimable material layer 230 is used as a third mask layer to form a third organic material layer 330 patterned in the plurality of third pixel regions of the substrate 100. can do. That is, a patterned third organic material layer 330 may be formed in the plurality of third opening regions H30 corresponding to the plurality of third pixel regions. The patterned third organic material layer 330 may have a shape defined by the third sublimable material layer 230 . While forming the patterned third organic material layer 330, at least a portion of the third sublimable material layer 230 may be sublimated. The patterned third organic material layer 330 may correspond to the thin film 30 of FIG. 1B, and the thickness, formation method, etc. of the patterned third organic material layer 330 are similar to those of the patterned third organic material layer 330 of FIG. 3C. 1 It may be the same or similar to what was described for the organic material layer 310.

The patterned third organic material layer 330 may be a third organic light-emitting layer. The third organic light-emitting layer may be any one of a red (R) light-emitting layer, a green (G) light-emitting layer, and a blue (B) light-emitting layer of an organic light-emitting device (OLED). For example, the third organic light-emitting layer may be a blue light-emitting layer. In this case, any organic material used in the blue light-emitting layer of a general organic light-emitting device (OLED) may be used as the material for the third organic light-emitting layer.

The entire third sublimable material layer 230 may be removed by sublimation. FIG. 3J shows a state in which the entire third sublimable material layer 230 in FIG. 3I has been removed. As shown in FIG. 3J, a patterned third organic material layer 330 may be formed on the substrate 100. The third patterned organic material layer 320 may be disposed adjacent to the first patterned organic material layer 310 and the second patterned organic material layer 320. The first to third organic material layers 310, 320, and 330 can be said to constitute one 'light-emitting layer'.

Thereafter, although not shown, an upper structure including a predetermined organic layer and an electrode may be further formed on the first to third organic material layers 310, 320, and 330.

According to an embodiment of the present invention, the patterned first to third organic material layers 310, 320, and 330 can be easily formed using a new method using a sublimable material rather than a vacuum deposition method using a conventional MM. . Therefore, various problems and limitations of the existing thin film formation method using MM can be overcome, and organic light emitting devices (OLEDs) with excellent performance and high resolution can be easily manufactured.

4A to 4E are cross-sectional views illustrating a method of manufacturing an organic light emitting device (OLED) by applying a thin film forming method according to an embodiment of the present invention.

Referring to FIG. 4A, the first electrode member 111 may be formed on a predetermined substrate 101. The substrate 101 may be a transparent substrate such as a glass substrate. In addition to glass, other materials such as transparent polymers may also be used as materials for the substrate 101. The first electrode member 111 may include a plurality of first electrode elements 11. For example, the plurality of first electrode elements 11 may be arranged side by side while extending in the first direction. The plurality of first electrode elements 11 may be arranged to respectively correspond to the plurality of pixel areas P1, P2, and P3.

Next, the hole injection layer 121 and the hole transport layer 131 may be sequentially formed on the first electrode member 111. The hole injection layer 121 and the hole transport layer 131 may be formed entirely to cover the plurality of pixel areas (P1, P2, and P3).

Although not shown, in some cases, the space between the plurality of first electrode elements 11 may be filled with an insulating material. Alternatively, a portion of the hole injection layer 121 may be provided to fill the space between the plurality of first electrode elements 11.

The first pixel area P1 may be a red pixel area, the second pixel area P2 may be a green pixel area, and the third pixel area P3 may be a blue pixel area. The following description is based on the case where the first pixel area P1 is a red pixel area, the second pixel area P2 is a green pixel area, and the third pixel area P3 is a blue pixel area. However, the colors displayed by the first to third pixel areas (P1, P2, and P3) may vary.

Referring to FIG. 4B, the first organic light emitting layer 311 disposed corresponding to the first pixel area P1 may be formed on the hole transport layer 131. The method of forming the first organic light emitting layer 311 may be the same or similar to the method of forming the first organic material layer 310 described with reference to FIGS. 3B to 3D. That is, the first organic light-emitting layer 311 may be formed using the first sublimable material layer (not shown) as a mask layer. The first organic light-emitting layer 311 may correspond to the first organic material layer 310 of FIG. 3D.

Referring to FIG. 4C, a second organic light emitting layer 321 disposed corresponding to the second pixel area P2 may be formed on the hole transport layer 131. The method of forming the second organic light emitting layer 321 may be the same or similar to the method of forming the second organic material layer 320 described with reference to FIGS. 3E to 3G. That is, the second organic light-emitting layer 321 may be formed using the second sublimable material layer (not shown) as a mask layer. The second organic light-emitting layer 321 may correspond to the second organic material layer 320 of FIG. 3G.

Referring to FIG. 4D, a third organic light emitting layer 331 disposed corresponding to the third pixel area P3 may be formed on the hole transport layer 131. The method of forming the third organic light emitting layer 331 may be the same or similar to the method of forming the third organic material layer 330 described with reference to FIGS. 3H to 3J. That is, the third organic light-emitting layer 331 may be formed using the third sublimable material layer (not shown) as a mask layer. The third organic light-emitting layer 331 may correspond to the third organic material layer 330 of FIG. 3J. The first to third organic light emitting layers 311, 321, and 331 may be collectively referred to as one light emitting layer 301.

Referring to FIG. 4E, the electron transport layer 411 and the electron injection layer 421 may be sequentially formed on the light emitting layer 301. The electron transport layer 411 and the electron injection layer 421 may be formed entirely to cover the plurality of pixel areas (P1, P2, and P3).

Next, the second electrode member 431 may be formed on the electron injection layer 421. The second electrode member 431 may include a plurality of second electrode elements 21. Here, for convenience, the plurality of second electrode elements 21 are shown extending in the same direction as the plurality of first electrode elements 11, but the plurality of second electrode elements 21 are formed as a plurality of first electrode elements. It may have a structure extending in a direction different from (11), that is, in the second direction. The plurality of second electrode elements 21 may extend in a direction perpendicular to the plurality of first electrode elements 11.

In the device structure of FIG. 4E, the part corresponding to the first pixel area P1 can be referred to as a ‘first pixel unit’, and the part corresponding to the second pixel area P2 can be referred to as a ‘second pixel unit.’ The portion corresponding to the third pixel area P3 may be referred to as a ‘third pixel portion.’

5 and 6 are photographic images showing a case in which a sublimable material layer is formed on a glass substrate according to an exemplary embodiment of the present invention.

Referring to FIG. 5, a first sublimable material layer pattern 2a may be formed in the central portion of the glass substrate 1. The first sublimable material layer pattern 2a may be formed through a solution process. More specifically, after preparing a naphthalene solution (naphthalene content: 25 wt%) in which naphthalene is dissolved in benzene, the naphthalene solution is applied (or printed) in a predetermined shape to the center of the glass substrate 1. 1 A sublimable material layer pattern 2a can be formed. However, the specific method of forming the first sublimable material layer pattern 2a disclosed herein is merely illustrative and may be varied in various ways. For example, the first sublimable material layer pattern 2a may be formed through a PVD process rather than a solution process.

Referring to FIG. 6, it can be seen that a portion of the first sublimable material layer pattern 2a formed in the center of the glass substrate 1 begins to sublimate at room temperature. Additionally, in Figure 6, a second sublimable material layer pattern 2b can be seen newly formed below the first sublimable material layer pattern 2a.

Figure 7 shows an exemplary embodiment of the present invention, in which a sublimable material layer is formed on a glass substrate and then a patterned thin film is formed on the glass substrate using the sublimable material layer as a mask. This is a photographic image showing.

Referring to FIG. 7, a patterned thin film 3 is formed on the glass substrate 1 using the first and second sublimable material layer patterns 2a and 2b described in FIGS. 5 and 6 as masks. You can. It can be seen that the patterned thin film 3 has a shape/pattern defined by the sublimable material layer patterns 2a and 2b. At this time, the patterned thin film 3 may include Alq ₃ corresponding to a green light-emitting organic material. Here, Alq ₃ represents tris(8-hydroxyquinolinato)aluminium. When forming the patterned thin film 3, the process conditions were as follows.

< Process conditions >

* Shower head temperature: 350℃

* Carrier gas temperature: 350℃

* Source temperature: 320℃

* Chamber pressure: 1.2 Torr

* Substrate temperature: 20℃

* Carrier gas type: N ₂

* Carrier gas flow rate: 550 sccm

*Gap between shower head and substrate: 82 mm

* Deposition time: 10 sec

Figure 7 shows the results of an exemplary and tentative experiment, and the precision of pattern formation can be secured by controlling the experiment method and conditions.

According to the embodiments of the present invention described above, a thin film forming method capable of forming a patterned material film (thin film) in a new way without using a metal mask such as a conventional MM (metal mask) can be implemented. . Therefore, by using the thin film forming method according to the embodiment, various problems and limitations of the existing thin film forming method using MM can be overcome. Additionally, according to embodiments of the present invention, various electronic devices can be easily manufactured using the thin film forming method described above. In particular, using the thin film formation method described above, organic light emitting devices (OLEDs) with excellent performance and high resolution can be more easily manufactured.

In addition, in this description, the top-down method in which the deposition source is located at the top and the substrate is located at the bottom is described, but the bottom-up method is used in which the deposition source is located at the bottom and the substrate is located at the top. up) method and the vertical method in which the deposition source and the substrate are positioned perpendicularly, the spirit of the embodiment of the present invention can be easily applied.

In this specification, preferred embodiments of the present invention are disclosed, and although specific terms are used, they are merely used in a general sense to easily explain the technical content of the present invention and aid understanding of the invention, and do not define the scope of the present invention. It is not intended to be limiting. It is obvious to those skilled in the art that in addition to the embodiments disclosed herein, other modifications based on the technical idea of the present invention can be implemented. Those of ordinary skill in the art will understand that the thin film formation method and the device manufacturing method using the same according to the embodiments described with reference to FIGS. 1A to 7 may vary without departing from the technical spirit of the present invention. It will be appreciated that it can be substituted, changed, and modified. Therefore, the scope of the invention should not be determined by the described embodiments, but by the technical idea stated in the patent claims.

* Explanation of symbols for main parts of the drawing *
10: Substrate 20: Sublimable material layer
30: thin film 100: substrate portion
101: substrate 111: first electrode member
121: hole injection layer 131: hole transport layer
210: first sublimable material layer 220: second sublimable material layer
230: Third sublimable material layer 301: Light-emitting layer
310: first organic material layer 311: first organic light-emitting layer
320: second organic material layer 321: second organic light-emitting layer
330: third organic material layer 331: third organic light-emitting layer
411: electron transport layer 421: electron injection layer
431: Second electrode member P1: First pixel area
P2: Second pixel area P3: Third pixel area

Claims (22)

A method of forming a patterned thin film, comprising:
forming a layer of sublimable material on a portion of the substrate; and
Comprising the step of using the sublimable material layer as a mask layer to form a thin film on an area of the substrate where the sublimable material layer is not formed,
The thin film has a pattern defined by the layer of sublimable material,
When forming the thin film, the temperature of the substrate is adjusted to 10 ° C to 90 ° C,
While forming the thin film, at least a portion of the sublimable material layer is sublimated, the thin film is not deposited on the sublimable material layer, and the thin film is selectively deposited only on areas of the substrate where the sublimable material layer is not formed. And
The step of forming the thin film is performed using deposition equipment in which a supply part of the source material for deposition of the thin film is disposed above the substrate, and when the source material reaches the surface of the substrate, the source material is A method of forming a patterned thin film, wherein the thin film is deposited at a temperature ranging from 180° C. to 250° C. According to claim 1,
The method of forming a patterned thin film, wherein the sublimable material layer includes a material having a melting point in the range of 60° C. to 210° C. at 1 atm. According to claim 1,
A method of forming a patterned thin film wherein the sublimable material layer includes an aromatic hydrocarbon compound. According to claim 3,
The aromatic hydrocarbon compounds include naphthalene, anthracene, 9-Methylanthracene, 2-Methylanthracene, and 9,10-dimethylanthracene. A method of forming a patterned thin film containing at least one of , phenanthrene, and 3-methylphenanthrene. According to claim 1,
A method of forming a patterned thin film, wherein the sublimable material layer is formed to a thickness of 1 nm to 10 ㎛. According to claim 1,
A method of forming a patterned thin film in which the sublimable material layer is formed using a PVD method, a printing method based on a solution process, or a coating method based on a solution process. According to claim 1,
A method of forming a patterned thin film, wherein the thin film includes an organic material. According to claim 7,
A method of forming a patterned thin film, wherein the thin film includes an organic light-emitting material. According to claim 1,
A method of forming a patterned thin film in which the thin film is formed using a PVD method. delete According to claim 1,
A method of forming a patterned thin film wherein the entire sublimable material layer is removed by sublimation. Forming a thin film on a substrate using the method according to any one of claims 1 to 9 and 11; and
A method of manufacturing an electronic device comprising manufacturing an electronic device including the thin film. A method of manufacturing an organic light-emitting device having a plurality of pixel portions,
forming a first layer of sublimable material on a substrate having a plurality of first open areas corresponding to a plurality of first pixel areas; and
forming a patterned first organic material layer in the plurality of first pixel regions of the substrate using the first sublimable material layer as a first mask layer;
wherein the patterned first organic material layer has a shape defined by the first sublimable material layer,
When forming the patterned first organic material layer, the temperature of the substrate is adjusted to 10 ° C to 90 ° C,
While forming the patterned first organic material layer, at least a portion of the first sublimable material layer is sublimated, the first organic material layer is not deposited on the first sublimable material layer, and the first sublimable material layer is not deposited on the first sublimable material layer. The patterned first organic material layer is selectively deposited only on areas of the substrate where a sublimable material layer is not formed,
The step of forming the patterned first organic material layer is performed using deposition equipment in which a supply part of a source material for deposition of the patterned first organic material layer is disposed above the substrate, wherein the source material A method of manufacturing an organic light-emitting device in which the patterned first organic material layer is deposited such that the temperature of the source material is in the range of 180°C to 250°C when it reaches the surface of the substrate. According to claim 13,
The first sublimable material layer is Naphthalene, Anthracene, 9-Methylanthracene, 2-Methylanthracene, 9,10-Dimethylanthracene ), Phenanthrene, 3-Methylphenanthrene A method of manufacturing an organic light-emitting device comprising at least one of the following. According to claim 13,
A method of manufacturing an organic light-emitting device, wherein the first sublimable material layer is formed to a thickness of 1 nm to 10 ㎛. According to claim 13,
A method of manufacturing an organic light-emitting device, wherein the patterned first organic material layer is a first organic light-emitting layer. delete According to claim 13,
A method of manufacturing an organic light emitting device in which the entire first sublimable material layer is removed by sublimation. According to claim 13,
After forming the patterned first organic material layer,
forming a second sublimable material layer covering the patterned first organic material layer on the substrate, the second layer of sublimable material having a plurality of second open areas corresponding to a plurality of second pixel areas; and
The method of manufacturing an organic light emitting device further comprising forming a patterned second organic material layer in the plurality of second pixel regions of the substrate using the second sublimable material layer as a second mask layer. According to claim 19,
A method of manufacturing an organic light-emitting device, wherein the patterned second organic material layer is a second organic light-emitting layer. According to claim 19,
After forming the patterned second organic material layer,
forming a third sublimable material layer covering the patterned first and second organic material layers on the substrate, the third layer of sublimable material having a plurality of third open regions corresponding to a plurality of third pixel regions; and
The method of manufacturing an organic light-emitting device further comprising forming a patterned third organic material layer in the plurality of third pixel regions of the substrate using the third sublimable material layer as a third mask layer. According to claim 21,
A method of manufacturing an organic light-emitting device, wherein the patterned third organic material layer is a third organic light-emitting layer.