KR20160103589A - Passivation film for organic electronic devices and Method for depositing the same - Google Patents

Abstract

The present invention relates to a passivation film for an organic electronic device and a method of depositing the same, and more particularly, to a passivation film for an organic electronic device which is capable of effectively blocking moisture or oxygen and a method of depositing the same. The passivation film formed on an organic electronic device includes a barrier film having a composition layer of SiO_x1C_y1 (x1>0, y1>0); and a buffer film having a composition layer of SiO_x2C_y2 (x2>0, y2>0), wherein the barrier film and the buffer film may be alternately stacked.

Description

TECHNICAL FIELD [0001] The present invention relates to a protective film for organic electronic devices and a method for depositing the organic electronic device.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a protective film for an organic electronic device and a deposition method thereof, and more particularly, to a protective film for an organic electronic device capable of effectively blocking moisture or oxygen and a deposition method thereof.

Organic electronic devices such as organic light emitting diodes (OLEDs), organic solar cells, and organic thin film transistors (organic TFTs) are vulnerable to moisture and oxygen, and require a sealing process to protect the devices. Here, the protective film for an organic electronic device is required not only to protect the device but also to have a flexible characteristic.

For this reason, conventionally, an inorganic film for preventing moisture permeation and an organic film for flexibility are laminated and used. In order to sequentially laminate a multilayer structure film of an inorganic film and an organic film, a plurality of chambers must be deposited, A mask is required. In addition, since the organic film is easily permeable to moisture, the moisture permeates to the exposed side surface of the organic film, and the moisture permeates into the organic electronic device through the pinhole formed in the inorganic film. Since the inorganic film is hard, it is easily broken or the flexibility characteristic of the protective film for organic electronic devices is lowered.

In order to solve the problem of moisture permeating the organic film, Korean Patent Laid-Open No. 10-2013-0040574 (2013.04.24) discloses a method of completely covering the organic film by making the area of the inorganic film deposited on the organic film wider than that of the organic film However, since the deposition is still performed in a large number of chambers, there is a problem in that the size of the equipment is increased and a plurality of masks must be used. In addition, since the ratio of the inorganic film to the organic film is increased in the protective film for the organic electronic device, the flexibility characteristic of the protective film for the organic electronic device is also deteriorated.

Korean Patent Publication No. 10-2013-0040574

The present invention can deposit a barrier film and a buffer film by controlling only x and y in the composition of SiO _x C _y , and can deposit the barrier film and the buffer film in the same chamber in a multilayer structure, A protective film for an electronic device and a deposition method thereof are provided.

A protective film for an organic electronic device according to an embodiment of the present invention is a protective film formed on an organic electronic device, and includes a barrier film having a composition layer of SiO _{x 1} C _y1 (x1> 0, y1>0); And _{SiO x2 C y2 (x2> 0} , y2> 0) may be included in the buffer film having a composition layer, film alternately stacking the barrier layer and the buffer.

The x1 may be greater than the x2 and the y1 may be less than the y2.

The content of carbon in the barrier film may be 1 to 5 at%.

The buffer film may have a carbon content of 5 to 50 at%.

The barrier film and the buffer film may have the same area.

The buffer layer may have a thickness of 200 to 2000 ANGSTROM.

The barrier layer may have a thickness of 200 to 5000 ANGSTROM.

And an auxiliary barrier film contacting at least one surface of the buffer film and having a composition layer of SiN _z .

The buffer layer may be disposed between the barrier layer and the auxiliary barrier layer.

According to another aspect of the present invention, there is provided a method for depositing a protective film for an organic electronic device, comprising: loading a substrate on which an organic electronic device is formed into a chamber; A laminated structure of a buffer film having a composition layer of SiO _{x 1} C _y1 (x1> 0, y1> 0) and a buffer layer having a composition layer of SiO _x2 C _y2 (x2> 0, y2> 0) step; And unloading the substrate from the chamber, wherein forming the laminate structure may be performed in a single chamber.

The forming of the laminated structure may be performed by alternately laminating the barrier film and the buffer film a plurality of times, and the source material for deposition of the barrier film and the buffer film may be an organic silicon compound.

The step of forming the laminated structure may be performed while supplying a process gas containing oxygen atoms (O).

In the step of forming the laminated structure, a first condition that the supply amount of the raw material is larger than that when the barrier film is deposited in the case of depositing the buffer film, and a first condition that the supply amount of the process gas is made smaller than that when the barrier film is deposited 2 may be applied to deposit the buffer layer.

The step of forming the laminated structure may be performed by forming a plasma in the chamber, and when the buffer layer is deposited, the buffer layer may be deposited by weakening the intensity of the plasma compared with the deposition of the barrier layer.

In the step of forming the laminated structure, the barrier film and the buffer film can be laminated with a single mask.

A protective film for an organic electronic device according to another embodiment of the present invention is a protective film formed on an organic electronic device, including: a barrier film having a composition layer of SiO _{x 1} C _y1 (x1> 0, y1>0); Buffer layer having a composition of _{SiO x2 C y2 (x2> 0} , y2> 0) layer; And an auxiliary barrier film containing silicon (Si) and nitrogen (N), and the barrier film, the buffer film, and the auxiliary barrier film may be alternately stacked a plurality of times.

The auxiliary barrier film may further contain oxygen (O) and carbon (C) to have a composition of SiONC.

The raw material for the deposition of the auxiliary barrier film may include HMDSO.

The protective film for an organic electronic device according to an embodiment of the present invention can be alternately laminated with the barrier film and the buffer film only by adjusting x and y in the composition of SiO _x C _y so that deposition can be easily performed in a single chamber. Since the thickness of the buffer layer can be reduced by using the plasma, the exposed area can be reduced. Therefore, the barrier layer and the buffer layer can be stacked in a predetermined size and shape. As a result, the barrier layer and the buffer layer can be alternately stacked . Thus, the deposition equipment can be simplified and miniaturized, and the production cost can be reduced.

Since the barrier film contains carbon, the elasticity of the barrier film can be improved, so that the flexibility of the organic electronic device can be ensured and the defect of the barrier film made of an inorganic film, which is hard and easily broken, can be compensated.

Further, if the auxiliary barrier film is further included, the effect of preventing moisture permeation can be further improved.

The method of depositing a protective film for an organic electronic device according to another embodiment of the present invention can easily adjust the x and y of SiO _x C _y composition in a single chamber using HMDSO as a raw material, Can be stacked. By using the process gas containing nitrous oxide (N ₂ O) to oxidize the carbon, the ratio of carbon in the SiO _x C _y composition can be more effectively controlled. On the other hand, x and y of SiO _x C _y composition can be easily controlled by varying plasma intensity and N 2 O gas flow rate in PECVD equipment. When the output of the plasma is increased, the silicon (Si) and CH group bonding of HMDSO can be further decomposed, so that the ratio of carbon (C) can be decreased. When the flow rate of the nitrous oxide gas is increased, The ratio may be increased.

1 is a cross-sectional view illustrating a protective film for an organic electronic device according to an embodiment of the present invention.
FIG. 2 illustrates the molecular structure of HMDSO according to an embodiment of the present invention. FIG.
3 is a sectional view showing a modification of the protective film for an organic electronic device according to an embodiment of the present invention.
4 is a flowchart illustrating a method of depositing a protective film for an organic electronic device according to another embodiment of the present invention.
5 is a conceptual view showing a particle coating characteristic of a buffer film according to another embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. It will be apparent to those skilled in the art that the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, It is provided to let you know. In the description, the same components are denoted by the same reference numerals, and the drawings are partially exaggerated in size to accurately describe the embodiments of the present invention, and the same reference numerals denote the same elements in the drawings.

1 is a cross-sectional view illustrating a protective film for an organic electronic device according to an embodiment of the present invention.

1, a protective film for an organic electronic device according to an embodiment of the present invention is a protective film formed on an organic electronic device, and includes a barrier film having a composition layer of SiO _{x 1} C _y1 (x1> 0, y1> 0) (110); And a _{SiO x2 C y2 (x2> 0} , y2> 0) including the buffer film 120 having a composition layer, and the barrier film 110 and the buffer film 120 of the subject an alternating stacking.

The barrier layer 110 serves to prevent penetration of oxygen and moisture, and may have a composition layer of SiO _{x 1} C _y1 (x1> 0, y1> 0). The barrier film 110 may be formed in a manner similar to an inorganic film having excellent moisture barrier properties by adjusting the content of oxygen and carbon in order to enhance the moisture permeation preventing property.

An inorganic film such as SiO ₂ conventionally used as a barrier film is excellent in moisture permeation preventing property but is hard to apply because it is fragile because it is not flexible and is not suitable for a flexible display and is not suitable for a roll to roll process. However, as in the present invention, when y1 is greater than 0 in the composition of SiO _{x 1} C _y1 and carbon is contained in the barrier film 110, the flexibility of the barrier film 110 is improved because the carbon component provides elasticity. Accordingly, it is possible to secure the flexibility characteristic of the protective film for an organic electronic device, to be easily applied to a flexible display or the like, and to be suitable for a roll-to-roll process. And the pinhole growth caused by the inorganic film which is not flexible and is fragile can be suppressed. However, if the amount of carbon is too large, the moisture barrier property of the barrier film 110 is deteriorated, so that it is necessary to appropriately adjust the content (or y1) of carbon.

On the other hand, the content of carbon in the barrier film 110 can be selected in the range of 1 to 5 at%. When the carbon content of the barrier film 110 is less than 1 at%, the barrier film 110 has a hard and brittle property like an inorganic film, and cracks are likely to occur. On the other hand, if the carbon content of the barrier film 110 is larger than 5 at%, moisture can be permeated into the barrier film 110 like an organic film, which adversely affects the organic electronic device. If the barrier film 110 contains 1 to 5 at% of carbon, cracking of the barrier film 110 can be prevented while effectively preventing moisture permeation, and flexibility of the protective film for organic electronic devices can be ensured.

The buffer film 120 relaxes the stress of the barrier film 110, imparts flexibility to the protective film for organic electronic devices, flattens the protective film for organic electronic devices, and suppresses pinhole growth of the protective film for organic electronic devices do. The buffer film 120 may have a composition layer of SiO _{x 2} C _{y 2} (x 2 > 0, y 2 > 0) and may change y 2 to control the flexibility characteristics of the protective film for organic electronic devices. When the content of carbon in the buffer film 120 is increased, the flexibility characteristics can be improved. However, since the proportion of other elements is decreased, other characteristics are degraded, so that the content of carbon (or y2) needs to be appropriately controlled.

On the other hand, the content of carbon in the buffer film 120 can be selected in the range of 5 to 50 at%. If the carbon content of the buffer film 120 is less than 5 at%, the buffer film 120 is not soft enough to relieve the stress of the barrier film 110 and sufficiently provide the flexibility characteristic of the protective film for organic electronic devices can not do it. On the other hand, if the carbon content of the buffer film 120 is greater than 50 at%, the content of silicon (Si) in the buffer film 120 becomes small, which makes it difficult to form a SiO _{x 2} C _y2 thin film, The buffer characteristics for relieving the stress of the film 110 are degraded. If the buffer film 120 contains 5 to 50 at% of carbon, the buffer film 120 can be formed well while effectively providing the flexibility characteristic of the protective film for organic electronic devices.

The x1 may be greater than the x2 and the y1 may be less than the y2. That is, the carbon content of the buffer film 120 may be larger than the carbon content of the barrier film 110, and the oxygen content of the barrier film 110 may be larger than the oxygen content of the buffer film 120. If the carbon content of the barrier film 110 is large, it is impossible to prevent the external moisture from penetrating into the inside. Therefore, the carbon content of the barrier film 110 should be 5 at% or less, and the buffer film 120 is excellent in ductility It is necessary to provide at least 5 at%, which is more carbon content than the barrier film 110, in order to effectively provide the flexibility characteristic of the protective film for the organic electronic device. At this time, if the carbon content of the barrier film 110 and the carbon content of the buffer film 120 are equal to 5 at%, the barrier film 110 and the buffer film 120 become similar and pinhole growth can not be suppressed, Can not be prevented from penetrating into the inside. Therefore, the y1 may be smaller than the y2. Since the SiO _x C _y film can be dense if the content of oxygen in the composition of SiO _x C _y is increased, the oxygen content of the barrier film 110, which is mainly required to have a moisture barrier property, is larger than the oxygen content of the buffer film 120 Can be many. That is, x1 may be greater than x2. On the other hand, x1 may be adjusted to 1.5 to 2, y1 to 0 to 0.5, x2 to 1.0 to 1.5, and y2 may be adjusted to 0.5 to 1.0 while satisfying the above conditions.

In general, when the organic layer and the inorganic layer are alternately stacked, a plurality of chambers are required because the organic layer and the inorganic layer must be deposited in different chambers. The barrier layer 110 and the buffer layer 120 of the present invention are basically Since it is a thin film containing silicon, oxygen and carbon, it is possible to alternately laminate in a single chamber without requiring a plurality of chambers, and it is possible to alternately stack x and y only in SiO _x C _y composition, 110 and the buffer layer 120 can be formed. Therefore, since it is not necessary to deposit in a large number of chambers, the equipment can not be made large, the productivity can be increased, and the production cost can be reduced. The barrier film 110 and the buffer film 120 may be deposited first so that the barrier film 110 is in contact with the organic electronic device and the buffer film 120 may be bonded to the organic electronic device. The buffer film 120 may be deposited first, but it is preferable that the barrier film 110 having excellent moisture barrier properties is formed in contact with the organic electronic device. And a protective film for the organic electronic device is formed on the substrate 10 so as to completely cover the organic electronic device.

Since the conventional buffer film is deposited using the solution method, a thickness of 0.5 to 1 mu m is required for planarization of the protective film for organic electronic devices. Therefore, the conventional buffer film has a problem in that moisture permeates into a side surface of a large exposed area because the area of the side surface is inevitably widened. For this reason, conventionally, when forming a protective film for an organic electronic device, the barrier film and the buffer film can not be stacked alternately as a single mask, and the barrier film and the buffer film are alternately laminated while replacing the barrier film with a plurality of masks There was no. However, in the present invention, since the buffer layer 120 is formed by forming plasma in the vacuum chamber (for example, PECVD), the thickness of the buffer layer 120 can be reduced while having excellent buffering characteristics. The barrier film 110 and the buffer film 120 may be alternately stacked with a single mask.

The buffer layer 120 may have a thickness of 200 to 2000 ANGSTROM. In the present invention, since the SiO _{x 2} C _{y 2} thin film can be deposited using plasma, the buffer film 120 having a small thickness is also possible. However, if the thickness of the buffer film 120 becomes thinner than 200 ANGSTROM, the stress of the barrier film 110 can not be sufficiently mitigated, the degree of softening of the protective film for organic electronic devices is insufficient, Not only can not be planarized but also the pinhole growth of the protective film for organic electronic devices can not be suppressed. On the other hand, if the thickness of the buffer film 120 becomes thicker than 2000 ANGSTROM, it is possible to sufficiently impart flexibility to the protective film for organic electronic devices and planarize the protective film for organic electronic devices. However, The area of the side surface of the buffer film 120 is widened and moisture is permeated into the exposed side surface to adversely affect the organic electronic device. In particular, the buffer film 120 This problem occurs when the layers are laminated. On the other hand, when the thickness of the buffer film 120 is 500 ANGSTROM or less, the moisture permeable to the side surface can be blocked more effectively. Therefore, the overall thickness of the protective film for organic electronic devices can be reduced while securing the flexibility characteristic of the organic electronic device protective film, The thickness of the buffer film 120 may be selected in the range of 200 to 500 angstroms.

The barrier layer 110 may have a thickness of 200 to 5000 ANGSTROM. When the thickness of the barrier film 110 becomes thinner than 200 angstroms, barrier properties such as gas barrier property and water barrier property tend to be lowered. When the thickness of the barrier film 110 becomes thicker than 5000 angstroms, A crack is generated in the barrier film 110 and gas or moisture permeates due to such a crack, thereby adversely affecting the organic electronic device. On the other hand, when it is necessary to further increase flexibility of the organic electronic device for application to a flexible display or the like, or when it is necessary to limit the overall thickness of the organic electronic device protective film, the thickness of the barrier film 110 may be in the range of 200 to 2000 ANGSTROM You can choose.

2 is a diagram illustrating the molecular structure of HMDSO according to an embodiment of the present invention.

In one embodiment of the present invention, HMDSO (Hexamethyldisiloxane) can be used as a raw material for deposition of a SiO _x C _y film (that is, a barrier film and a buffer film). Referring to FIG. 2, (Si), oxygen (O), and carbon (C), which are components of the buffer layer 110 and the buffer layer 120, a SiO _x C _y film can be stably formed using a single raw material , And SiO _x C _y films including many CH groups are softened. On the other hand, nitrous oxide (N ₂ O) can be used to more effectively control oxygen and carbon.

FIG. 3 is a cross-sectional view showing a modification of the protective film for an organic electronic device according to an embodiment of the present invention, wherein FIG. 3A shows a protective film for an organic electronic device formed by a single mask, And a protective film for an organic electronic device.

Referring to FIG. 3, the barrier film 110 and the buffer film 120 may have the same area as shown in FIG. 3 (a). The meaning of the same area means that the side surfaces of the respective layers are formed as a single plane by being deposited with the same shape and width, and the barrier film 110 and the buffer film 120 can have the same area by stacking them with a single mask. The buffer layer 120 of the present invention has a thickness of 200-500 angstroms, although it is impossible to expose the side surface of the buffer layer due to the penetration of moisture through the side surface of the buffer layer due to the thickness of the thick buffer layer of 0.5-1. Since moisture can not penetrate into the side surfaces since they can be thinned, they can be laminated in the same area (i.e., in the same shape and width) to expose the side surface of the buffer film 120. [ Accordingly, the barrier film 110 and the buffer film 120 can be alternately stacked without replacing the mask using a single mask. Therefore, since the barrier film 110 and the buffer film 120 can be alternately laminated with a single mask, excellent mass productivity can be ensured and the production cost can be reduced. In order to prevent moisture from penetrating through the side surfaces of the buffer film 120, the barrier film 110 may be formed on the buffer layer 120, The film 120 may be completely covered.

In an embodiment of the present invention, the PECVD showerhead has an area of 375 mm × 375 mm, a substrate temperature of 60 to 80 ° C., a chamber vacuum of 0.5 Torr, an RF frequency of 13.56 or 27.12 MHz, an RF power of 300 to 1000 W The buffer film 120 is deposited by supplying HMDSO of bubbling with a carrier gas (for example, argon) in an amount of 50 to 100 sccm and a supply amount of nitrous oxide (N ₂ O) of 100 to 1000 sccm, The buffer layer 120 having a thickness of 200 to 500 ANGSTROM can be formed. Also, under the same conditions, the barrier layer 110 is deposited at a RF power of 500 to 1500 W, a supply amount of HMDSO bubbled with a carrier gas of 10 to 50 sccm, and a supply amount of nitrous oxide of 1000 to 3000 sccm, A barrier layer 110 can be formed. The barrier film 110 and the buffer film 120 were laminated to have a thickness of 500 Å in a predetermined size and shape using a single mask, and the moisture permeability was measured. As a result, the moisture permeability was measured as 0.008 g / m 2 · day or less . As described above, according to the present invention, a protective film for an organic electronic device having a low moisture permeability of 0.008 g / m 2 · day or less can be formed.

As shown in FIG. 3 (b), the protective film for organic electronic devices may further include an auxiliary barrier film 130 contacting at least one surface of the buffer film 120 and having a composition layer of SiN _z . The auxiliary barrier film 130 may contact at least one surface of the buffer film 120 and may have a composition layer of SiN _z . If the auxiliary barrier film 130 is further included, the effect of preventing moisture can be maximized. Since the film having the composition layer of SiN _z is an inorganic film, the auxiliary barrier film 130 having the composition layer of SiN _z is superior to the barrier film 110 in moisture permeation prevention property and the auxiliary barrier film 130 is formed of the organic electronic device 20), it is possible to maximize the effect of preventing moisture permeation. The auxiliary barrier layer 130 having the composition layer of SiN _z can be deposited using monosilane (SiH ₄ ) and ammonia (NH ₃ ) as the source gas. When monosilane and ammonia are used as the source gas, monosilane The components of ammonia are similar to those of HMDSO and nitrous oxide and can be deposited using plasma in the same chamber in which the barrier film 110 and the buffer film 120 are deposited. If necessary, the process gas and the raw material existing in the chamber may be purged between the SiN _z composition layer and the SiO _x C _y composition layer. While the auxiliary barrier film 130 is being deposited, oxynitriding gases such as HMDSO and nitrous oxide, nitrogen monoxide (NO), and nitrogen dioxide (NO ₂ ) together with monosilane (SiH ₄ ) and ammonia (NH ₃ ) It is also possible to make a SiONC composition layer by using it. Also, monosilane (SiH ₄ ) can be used for deposition of the barrier film 110 and the buffer film 120, and it can be used as an auxiliary gas for silicon that replenishes silicon (Si) in addition to HMDSO.

The buffer film 120 may be positioned between the barrier film 110 and the auxiliary barrier film 130 and stacked. In this case, since the buffer film 120 can absorb and alleviate both the stress of the barrier film 110 and the stress of the auxiliary barrier film 120, the flexibility characteristic of the protective film for organic electronic devices can be sufficiently secured can do.

In this case, the barrier film 110 may be formed between the auxiliary barrier film 130 and the buffer film 120. In this case, The order of stacking the barrier film 110, the buffer film 120, and the auxiliary barrier film 130 is not particularly limited in the above-described order, and the stacking order may be adjusted for efficient operation of the protective film for organic electronic devices.

According to one embodiment of the present invention, the area of the PECVD showerhead is 375 mm x 375 mm, the substrate temperature is 60 to 80 ° C, the chamber vacuum is 0.5 Torr, and the RF frequency is 13.56 or 27.12 MHz , The RF power was 200 to 600 W, the monosilane supply amount was 50 to 100 sccm, and the ammonia supply amount was 25 to 50 sccm to obtain a thickness of 200 to 2000 ANGSTROM. Here, the barrier layer 110 and the auxiliary barrier layer 130 were laminated to have a thickness of 500 angstroms in a predetermined size and shape using a single mask, and the moisture permeability was measured. As a result, 0.002 g / m 2 · day or less. At this time, the auxiliary barrier layer 130 having a thickness of 500 Å is stacked first so as to surround the organic electronic device, and the buffer layer 120 and the barrier layer 110 are stacked in this order. In the case of using the film 110, since the thickness of the film serving as a barrier (i.e., the barrier film and the auxiliary barrier film) becomes thick, the thickness of the auxiliary barrier film 130 , 500 Å), the thickness of the barrier layer 110 may be set to 300 Å or less. As described above, in the present invention, the barrier film 110 and the auxiliary barrier film 130 may be laminated together with a film serving as a barrier to form a protective film for an organic electronic device having a moisture permeability as low as 0.002 g / m 2 · day or less.

Since the protective film for organic electronic devices of the present invention can be deposited in a single chamber from a single mask, the equipment can be miniaturized and the process can be simplified, thereby increasing the productivity and reducing the production cost, In-situ cleaning of the chamber and mask after the process is also possible.

4 is a flowchart illustrating a method of depositing a protective film for an organic electronic device according to another embodiment of the present invention.

Referring to FIG. 4, a method of depositing a protective film for an organic electronic device according to another embodiment of the present invention will be described in more detail. The method for forming the protective film for an organic electronic device according to an embodiment of the present invention, Are omitted.

According to another embodiment of the present invention, there is provided a method of depositing a protective film for an organic electronic device, comprising: (S100) loading a substrate on which an organic electronic device is formed, into a chamber; A laminated structure of a buffer film having a composition layer of SiO _{x 1} C _y1 (x1> 0, y1> 0) and a buffer layer having a composition layer of SiO _x2 C _y2 (x2> 0, y2> 0) Step S200; And unloading the substrate from the chamber (S300).

First, the substrate on which the organic electronic device is formed is loaded into the chamber (S100). A protective film for the organic electronic device is deposited such that the organic electronic device is completely covered on the substrate loaded in the chamber. In this case, a mask (for example, a shadow mask) may be used to deposit a protective film for an organic electronic device in a predetermined area. In the case of using a shadow mask, after the substrate is loaded, As shown in FIG. Thereafter, the deposition is performed.

Next, a laminated structure of a barrier film having a composition layer of SiO _{x 1} C _y1 (x1> 0, y1> 0) and a buffer film having a composition layer of SiO _x2 C _y2 (x2> 0, y2> 0) (S200). The step of forming the laminated structure (S200) may be performed by alternately laminating the barrier film and the buffer film a plurality of times. At this time, it is possible to alternately laminate the barrier film and the buffer film more than 20 times so that the barrier film and the buffer film are more than 20 layers. In the present invention, this process can be performed with a single mask in a single chamber. Conventionally, in order to realize a foldable OLED, the thickness of the barrier film is reduced and the barrier film and the buffer film are formed into five layers (three layers of barrier film and two layers of buffer film) or seven layers (four layers of barrier film and three layers of buffer film) However, since 5 or 7 chambers and shadow masks must be operated at this time, there is a disadvantage that the equipment becomes large and the productivity becomes low. However, in the present invention, since more layers can be stacked in a single chamber from a single mask, the size of the equipment can be reduced and the productivity can be increased. The barrier film serves to prevent penetration of oxygen and moisture, and may have a composition layer of SiO _{x 1} C _y1 (x1> 0, y1> 0). The barrier film may be formed in a manner similar to an inorganic film having excellent moisture permeation-preventing characteristics by adjusting oxygen and carbon in order to improve the moisture permeation preventing property. Here, the content of carbon in the barrier film may be 1 to 5 at%. When the carbon content of the barrier film is smaller than 1 at%, the barrier film has a hard and brittle property like an inorganic film, If the carbon content of the barrier film becomes larger than 5 at%, moisture can be permeated into the barrier film like an organic film, which adversely affects the organic electronic device. Therefore, if the barrier film contains 1 to 5 at% of carbon, cracking of the barrier film can be prevented effectively while moisture permeation is effectively prevented, and flexibility of the protective film for organic electronic devices can be secured.

The buffer film mitigates the stress of the barrier film, imparts flexibility to the protective film for the organic electronic device, flattenes the protective film for the organic electronic device, and also suppresses the pinhole growth of the protective film for the organic electronic device. The buffer film may have a composition layer of SiO _{x 2} C _y2 (x2 > 0, y2 > 0), and the flexibility characteristic of the protective film for organic electronic devices can be controlled by changing y2. Here, if the carbon content of the buffer film is less than 5 at%, the buffer film may have a carbon content of 5 to 50 at%. However, since the buffer film has a low ductility, stress of the barrier film can not be relieved, If the carbon content of the buffer film is greater than 50 at%, the content of silicon (Si) in the buffer film is decreased, which makes it difficult to form a thin film. Therefore, when the buffer film contains 5 to 50 at% of carbon, the buffer film can be formed well while effectively providing the flexibility characteristic of the protective film for organic electronic devices.

On the other hand, the order of stacking the barrier film and the buffer film is not particularly limited, and the stacking order can be determined for effective operation of the protective film for organic electronic devices.

The source material for deposition of the barrier film and the buffer film may be an organic silicon compound. Organic silicon compounds include silicon-containing organic materials such as HMDSO, HMDS, DMADMS, and BDMAMS. Since the organosilicon compound contains silicon (Si) and carbon (C), a large number of raw materials are not required, and in particular, HMDSO contains silicon (Si), oxygen (O) and carbon (C) HMDSO can be used to deposit a barrier film and a buffer film having a composition of SiO _x C _{y by} controlling only the supply amount as a single raw material, thereby alternately stacking the barrier film and the buffer film in a single chamber. Thus, the step of forming the laminated structure can be performed in a single chamber.

The step of forming the laminate structure (S200) may be performed while supplying a process gas containing oxygen atoms (O). The process gas may be at least one of oxygen (O ₂ ), oxynitriding gases such as nitrous oxide (N ₂ O), nitrogen monoxide (NO), nitrogen dioxide (NO ₂ ) By oxidizing, the ratio of carbon in SiO _x C _y composition can be controlled more effectively, and hydrogen atoms (H) can be removed by oxidation.

In this case, when a top cathode of the organic electronic device forms a protective film on the top cathode, such as a top emission OLED in which the emitted light is emitted in an upward direction of the OLED, oxygen (O ₂ ) The top cathode of the organic electronic device is oxidized. Therefore, an oxynitriding gas such as nitrous oxide, nitrogen monoxide, or nitrogen dioxide can be used without directly using oxygen. For example, when nitrous oxide is used, the carbon contained in the raw material can be effectively oxidized and the hydrogen atoms (H) can be removed without oxidizing the top cathode of the organic electronic device.

On the other hand, when the protective film is not formed on the top cathode of the organic electronic device, such as a bottom emission type OLED in which the emitted light is emitted in the lower direction of the OLED, there is no problem such as top cathode oxidation, .

In the step of forming the laminated structure (S200), a first condition that the supply amount of the raw material is larger than that when the barrier film is deposited, and a second condition that the supply amount of the process gas is less than that when the barrier film is deposited, May be applied to deposit the buffer film. Since the organic silicon compound as the raw material contains a large amount of carbon, the carbon content of the film (hereinafter, referred to as a deposition film) deposited increases as the amount of the raw material supplied increases. A vapor deposition film having a high carbon content (that is, an increased supply amount of the raw material) is suitable for use as a buffer film because a higher carbon content of the vapor deposition film improves the flexibility characteristics. On the other hand, the barrier film should prevent the penetration of oxygen and moisture, so the carbon content should not be high. Thus, the barrier film and the buffer film can be deposited by adjusting the supply amount of the raw material.

The process gas oxidizes the carbon contained in the raw material. When the amount of the process gas supplied is large, a large amount of the process gas oxidizes a large amount of carbon contained in the raw material, thereby reducing the carbon content of the deposited film. As described above, when the carbon content of the vapor-deposition film is small, the vapor-deposition characteristics of the vapor-deposited film disappear, the hardness is improved, and the moisture permeation prevention property is improved, so that the vapor-deposited film having a low carbon content (that is, a large amount of the process gas) is suitable for use as a barrier film. On the other hand, the buffer film must have a high carbon content because of its excellent flexibility properties. The barrier film and the buffer film may be deposited by adjusting the supply amount of the process gas.

As described above, the buffer film can have a superior flexibility property by increasing the supply amount of the raw material or reducing the supply amount of the process gas by increasing the carbon content as compared with the deposition of the barrier film. On the other hand, the first condition for increasing the supply amount of the raw material and the second condition for decreasing the supply amount of the process gas may be used at the same time, and if they are used simultaneously, the carbon content of the deposition film (that is, the barrier film or the buffer film) have. For example, increasing the gas flow rate of the process gas, nitrous oxide, can increase the proportion of oxygen (O) while lowering the carbon content.

The step of forming the laminated structure (S200) may be performed by forming a plasma in the chamber. In the PECVD deposition, a vapor deposition layer is deposited using a plasma, and the content of carbon contained in the thin layer can be controlled by controlling the plasma intensity. For example, when the output of plasma is increased, silicon (Si) and C-H group bonding of HMDSO, which is a raw material, can be further decomposed, so that the ratio of carbon (C) can be reduced.

In the case of depositing a buffer film, the buffer film can be deposited by weakening the intensity of the plasma as compared with the case of depositing the barrier film. When the barrier film is deposited, a strong plasma is generated so that the carbon contained in the raw material is almost completely oxidized. When the buffer film is deposited, a weak plasma is generated so that the carbon contained in the raw material may remain. When the carbon content of the buffer film is larger than 50 at% because plasma is not generated, the content of silicon (Si) in the buffer film is decreased, and the SiO _x C _y thin film is formed Because of difficulties. Therefore, a weaker plasma can be generated when the barrier film is deposited when the buffer film is deposited. On the other hand, when the plasma is generated, the RF output relative to the showerhead area may be 0.4 to 0.6 W / cm 2 for the barrier film and 0.2 to 0.4 W / cm 2 for the buffer film.

In the step of forming the laminated structure (S200), the barrier film and the buffer film may be stacked with a single mask. The mask causes the barrier film and the buffer film to be deposited in a predetermined pattern or shape, and may include a shadow mask and a photoresist mask. In order to planarize the protective film for organic electronic devices, the thickness of the buffer film has been increased to 0.5 to 1 占 퐉 because the buffer film is deposited by the solution method in the past. In the present invention, however, the protective film for the organic electronic device is planarized using the plasma, Can be made as thin as 200 to 500 ANGSTROM, so that it is possible to solve the problem that moisture permeates into the exposed side surface of a wide area. Since the side surface of the buffer layer is exposed, the barrier layer and the buffer layer can be stacked in a predetermined size and shape, and the barrier layer and the buffer layer can be stacked in a predetermined size and shape using a single mask. Therefore, in the present invention, the barrier film and the buffer film can be stacked with a single mask.

Finally, the substrate is unloaded from the chamber (S300). In the present invention, since all of the protective films for organic electronic devices are laminated in a single chamber, the laminated structure of the barrier film and the buffer film is formed, and then the substrate is unloaded from the chamber. Here, when using the shadow mask, a step of separating the shadow mask from the substrate may be performed before the substrate is unloaded from the chamber.

5 (a) is a view showing a conventional protective film for an organic electronic device, and Fig. 5 (b) is a cross-sectional view illustrating a protective film for an organic electronic device according to another embodiment of the present invention. (b) is a view showing the buffer film of the present invention first deposited, and FIG. 5 (c) is a view showing the deposition of the buffer film of the present invention after the barrier film.

5, when the barrier film 11 and the buffer film 12 are formed, when the particles 30, which are impurities, are present on the substrate 10 as shown in FIG. 5 (a), the particle- The barrier film 11 or the buffer film 12 is not deposited on the substrate 10 covered with the particle 30. In order to completely cover the particles, the buffer film has to be applied to a thickness of about 1 μm by a solution process, This forced the buffer membrane to thicken. However, since the buffer film 120 of the present invention has a composition of SiO _{x 2} C _{y 2} (x 2> 0, y 2> 0) using the organosilicon compound as a raw material, The portion between the particle 30 and the substrate 10 can be filled so that the buffer film 120 can be deposited on the substrate 10 covered with the particle 30 and the thickness of the buffer film 120 can also be reduced . Organosilicon compounds can be used as a raw material for the deposition of the buffer film 120. For example, HMDSO has a sticky property (or viscosity) as well as a good wettability, may be first adhered to the parts, and having a composition of particles (30) and to be able to fill the portion between the substrate _{(10) SiO x2 C y2 (} x2> 0, y2> 0) screened to a particle (30) by capillary action The buffer film can be deposited conformally. At this time, a pre-buffer layer (not shown) may be formed while only the HMDSO is supplied to the chamber without using nitrous oxide before the buffer layer 120 is deposited in order to secure the controllability more effectively. And, many CH groups contained in HMDSO can remain in the buffer film, so that the buffer film becomes more soft and the flexibility property is increased.

5 (c), the buffer layer 120 of the present invention is excellent in the particle coverage property, so that the barrier layer 110 is not deposited on the particles 30 between the particles 30 and the substrate 10. [0050] FIG. At this time, an organic silicon compound can be used as a raw material for the deposition of the buffer film 120, and in particular, HMDSO can be used. On the other hand, when HMDSO is used, since HMDSO is a liquid, it is bubbled into a carrier gas such as argon (Ar) and supplied into the chamber.

Hereinafter, a protective film for an organic electronic device according to another embodiment of the present invention will be described in detail. In the protective film for an organic electronic device and the method for depositing a protective film for an organic electronic device according to embodiments of the present invention, And redundant items are omitted.

A protective film for an organic electronic device according to another embodiment of the present invention is a protective film formed on an organic electronic device, including: a barrier film having a composition layer of SiO _{x 1} C _y1 (x1> 0, y1>0); Buffer layer having a composition of _{SiO x2 C y2 (x2> 0} , y2> 0) layer; And an auxiliary barrier film containing silicon (Si) and nitrogen (N), and the barrier film, the buffer film, and the auxiliary barrier film may be alternately stacked a plurality of times.

The composite protective film for organic electronic devices according to the present invention can maximize the effect of preventing moisture permeation by using the barrier film and the auxiliary barrier film together. The auxiliary barrier film may be an inorganic film containing no carbon. When the auxiliary barrier film is an inorganic film, the moisture barrier property is superior to that of the barrier film. If the auxiliary barrier film is brought into contact with the organic electronic device, the effect of preventing moisture permeation is maximized. The auxiliary barrier film can be deposited by using monosilane (SiH ₄ ) and ammonia (NH ₃ ) as the source gas. When monosilane and ammonia are used as the source gas, the monosilane and ammonia constitute the raw material of the barrier film and the buffer film Which is similar to the components of HMDSO and nitrous oxide, can be deposited using plasma in the same chamber as the barrier film and buffer chamber. If necessary, the process gas and the raw material existing in the chamber may be purged between the formation of the barrier film or the buffer film having the auxiliary barrier film and the composition layer of SiO _x C _y .

The auxiliary barrier film may further contain oxygen (O) and carbon (C) to have a composition of SiONC. When carbon is contained in the auxiliary barrier film, the composition can be similar to that of the barrier film and the buffer film, so that the material heterogeneity between the respective thin films is reduced, the deposition characteristics are enhanced, and the flexibility characteristics of the composite protective film for organic electronic devices are improved have. The auxiliary barrier film having the composition of SiONC can be prepared by using monosilane (SiH ₄ ) and ammonia (NH ₃ ) as the main raw material gas while simultaneously using HMDSO and nitrous oxide such as the raw materials of the barrier film and the buffer film, (NO ₂ ), or the like. Thus, the raw material for the deposition of the auxiliary barrier film may include HMDSO.

As described above, the protective film for an organic electronic device according to an embodiment of the present invention can alternately laminate the barrier film and the buffer film by adjusting x and y in the composition of SiO _x C _y , thereby enabling easy deposition in a single chamber. Since the thickness of the buffer layer can be reduced to 200 to 500 ANGSTROM by using plasma, the exposed area can be reduced, so that the barrier layer and the buffer layer can be stacked in a predetermined size and shape. As a result, It is possible to alternately stack the films. Thus, the deposition equipment can be simplified and miniaturized, and the production cost can be reduced. Since the barrier film contains carbon, the elasticity of the barrier film can be improved, so that the flexibility of the organic electronic device can be ensured and the defect of the barrier film made of an inorganic film, which is hard and easily broken, can be compensated. Further, if the auxiliary barrier film is further included, the effect of preventing moisture permeation can be further improved. The method of depositing a protective film for an organic electronic device according to another embodiment of the present invention can easily adjust the x and y of SiO _x C _y composition in a single chamber using HMDSO as a raw material, Can be stacked. By using the process gas containing nitrous oxide (N ₂ O) to oxidize the carbon, the ratio of carbon in the SiO _x C _y composition can be more effectively controlled. On the other hand, x and y of SiO _x C _y composition can be easily controlled by varying plasma intensity and N 2 O gas flow rate in PECVD equipment. When the output of the plasma is increased, the silicon (Si) and CH group bonding of HMDSO can be further decomposed, so that the ratio of carbon (C) can be decreased. When the flow rate of the nitrous oxide gas is increased, The ratio may be increased.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is clearly understood that the same is by way of illustration and example only and is not to be construed as limited to the embodiments set forth herein. Those skilled in the art will appreciate that various modifications and equivalent embodiments may be possible. Accordingly, the technical scope of the present invention should be defined by the following claims.

10: substrate 11, 110: barrier film
12, 120: Buffer film 20: Organic electronic device
30: Particle 130: Secondary barrier film

Claims (18)

As a protective film formed on an organic electronic device,
_{SiO x1 C y1 (x1> 0} , y1> 0) barrier layer having a composition layer; And
Containing film buffer layer having a composition of _{SiO x2 C y2 (x2> 0} , y2> 0) , and
Wherein the barrier film and the buffer film are alternately laminated.
The method according to claim 1,
X1 is larger than x2, and y1 is smaller than y2.
The method according to claim 1,
Wherein the barrier film has a carbon content of 1 to 5 at%.
The method according to claim 1,
Wherein the buffer film has a carbon content of 5 to 50 at%.
The method according to claim 1,
Wherein the barrier film and the buffer film have the same area.
The method according to claim 1,
Wherein the buffer layer has a thickness of 200 to 2000 ANGSTROM.
The method according to claim 1,
Wherein the barrier film has a thickness of 200 to 5000 ANGSTROM.
The method according to claim 1,
And an auxiliary barrier film contacting at least one surface of the buffer film and having a composition layer of SiN _z .
The method of claim 8,
Wherein the buffer film is disposed between and stacked on the barrier film and the auxiliary barrier film.
Loading a substrate on which an organic electronic device is formed into a chamber;
A laminated structure of a barrier film having a composition layer of SiO _{x 1} C _y1 (x1> 0, y1> 0) and a buffer layer having a composition layer of SiO _x2 C _y2 (x2> 0, y2>0); And
And unloading the substrate from the chamber,
Wherein the forming of the laminated structure is performed in a single chamber.
The method of claim 10,
The forming of the laminated structure may be performed by alternately laminating the barrier film and the buffer film a plurality of times,
Wherein the source material for deposition of the barrier film and the buffer film is an organic silicon compound.
The method of claim 11,
Wherein the step of forming the laminated structure is performed while supplying a process gas containing oxygen atoms (O).
The method of claim 12,
In the step of forming the laminated structure,
At least one of a first condition that the supply amount of the raw material is larger than that when the barrier film is deposited and a second condition that the supply amount of the process gas is made less than that when the barrier film is deposited in the case of depositing the buffer film And depositing the buffer layer.
The method of claim 10,
The forming of the laminated structure may be performed by forming a plasma in the chamber,
Wherein the buffer layer is deposited by weakening the intensity of the plasma when depositing the buffer layer, compared to depositing the barrier layer.
The method of claim 10,
Wherein the barrier film and the buffer film are laminated with a single mask in the step of forming the laminated structure.
As a protective film formed on an organic electronic device,
_{SiO x1 C y1 (x1> 0} , y1> 0) barrier layer having a composition layer;
Buffer layer having a composition of _{SiO x2 C y2 (x2> 0} , y2> 0) layer; And
And an auxiliary barrier film containing silicon (Si) and nitrogen (N)
Wherein the barrier film, the buffer film, and the auxiliary barrier film are laminated alternately a plurality of times.
18. The method of claim 16,
Wherein the auxiliary barrier film further contains oxygen (O) and carbon (C) and has a composition of SiONC.
18. The method of claim 17,
Wherein the raw material for the deposition of the auxiliary barrier film comprises HMDSO.

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