WO2014061532A1

WO2014061532A1 - Apparatus for depositing organic material

Info

Publication number: WO2014061532A1
Application number: PCT/JP2013/077523
Authority: WO
Inventors: 有紀今田
Original assignee: 富士フイルム株式会社
Priority date: 2012-10-17
Filing date: 2013-10-09
Publication date: 2014-04-24
Also published as: KR20150055062A; TWI591196B; JP5953280B2; TW201420786A; JP2014098207A

Abstract

Provided is an apparatus for depositing an organic material on a substrate in a vacuum environment. The deposition apparatus has: an evaporation chamber for heating and evaporating the organic material, the evaporation chamber being filled with the organic material; and a guide part for guiding to the substrate the organic material in the form of steam generated in the evaporation chamber. The evaporation chamber is continually maintained at a lower temperature than the guide part.

Description

Organic material deposition equipment

The present invention relates to an organic material vapor deposition apparatus that can be used for the manufacture of organic devices such as organic EL and organic CMOS, and in particular, without degrading the purity of the organic material, and further without decomposing the organic material. The present invention relates to a vapor deposition apparatus for an organic material that can be deposited with a composition.

In general, a vacuum heating vapor deposition method is used to form an organic material. For example, there are applications to organic devices such as organic EL and organic CMOS.
Conventional vapor deposition methods of organic materials include a point vapor deposition type and a line source type, in which a large amount of organic material is deposited in a vapor deposition crucible for vapor deposition. In addition to this, various vapor deposition apparatuses for organic materials have been proposed (Patent Documents 1, 2, etc.).

Patent Document 1 describes a vapor deposition apparatus for vapor-depositing an organic EL layer. In this vapor deposition apparatus, a crucible in which a film forming material is stored is in contact with the bottom wall of the second processing container to be evacuated, and heat in the container is released to the atmospheric system through the second processing container. Yes. As a result, the temperature in the vicinity of the portion of the crucible where the film forming material is stored is lower than or equal to the temperature of the other portion of the crucible.

Further, Patent Document 2 describes a vapor deposition apparatus that can continuously supply a thin film material and can form a film continuously for a long time. The vacuum vapor deposition apparatus of Patent Document 2 has a vacuum chamber in which a glass substrate can be installed and an evaporation apparatus having a heat generating part for evaporating a thin film material. The glass substrate is installed in the vacuum chamber and evaporated by the evaporation apparatus. The thin film material is evaporated to deposit a film of a predetermined component on the glass substrate. The heat generating part is located in a vacuum chamber or a position communicating with the vacuum chamber, and is disposed in a vacuum atmosphere when depositing a thin film. A thin film material feeding device that sends a thin film material from the outside of the vacuum chamber to the heat generating part is provided. Have. Cooling means for cooling the thin film material is provided upstream of the heat generating portion.

Here, as the organic material for the organic EL, a material having high heat resistance is basically used. For example, NPD (naphthyl-substituted diamine derivative) used for a hole transport material and Alq (hydroxyquinoline and aluminum complex) used for an electron transport material.

JP 2008-81778 A JP 2012-46814 A

If it is an organic material with high heat resistance, it can be vapor-deposited and formed into a film by placing an amount of organic material that can be continuously vaporized over several days in an evaporation crucible and an evaporation dish as in the conventional vapor deposition method. .
However, for example, when an organic material having a relatively low heat resistance is used as an organic material for organic CMOS, the above-described conventional vapor deposition method and the vapor deposition apparatus disclosed in Patent Documents 1 and 2 are heated for a long time or heat during heating. The purity or the like of the organic material is degraded by the load, or the organic material is decomposed. In such a state, there is a problem that the organic material cannot be used up in a pure state.

In addition, when an organic material is deposited, there are an organic material that jumps straight from the crucible or the like to the substrate, and an organic material that hits a side wall of the crucible or the like and repeatedly reflects and jumps out of the crucible or the like. At that time, if there is a low temperature area, for example, a vapor deposition device part having a low temperature on the vapor deposition path, the portion that reflects the organic material is reflected and becomes a cold spot. Once the organic material adheres to the cold spot, the organic material remains attached to the cold spot, or conversely, if the temperature of the cold spot rises to the material sublimation temperature and the organic material evaporates again, There is a problem that the heat load on the organic material becomes excessive.

The object of the present invention is to solve the problems based on the prior art, and to deposit an organic material that can be deposited with a stable composition without degrading the purity of the organic material and without further decomposing the organic material. To provide an apparatus.

In order to achieve the above object, the present invention is a vapor deposition apparatus for depositing an organic material on a film-forming material in a vacuum atmosphere, the organic material is disposed, and an evaporation chamber for heating and evaporating the organic material; An organic material vapor deposition apparatus characterized by having a guide portion for guiding the vapor of the organic material generated in the evaporation chamber to the film forming material, and the evaporation chamber is always kept at a lower temperature than the guide portion. It is to provide.
In this case, the heating method for the evaporation chamber is preferably an induction heating method.

It is preferable that the evaporation chamber has a filling portion in which an organic material is disposed at the bottom, and a heat dissipation member is provided at least at the bottom of the bottom and side surfaces of the filling portion.
For example, the heat dissipation member is a hollow cylindrical member and is directly connected to the filling portion. In this case, it is preferable that the heat radiating member is connected to the filling portion by welding.
In the evaporation chamber, it is preferable to have a control unit for controlling the temperature separately in the first region having the filling portion and the second region other than the filling portion.
When the heating method of the evaporation chamber is an induction heating method, the induction heating coil is arranged in the evaporation chamber so that the pitch of the second region other than the filling portion is narrower than the pitch of the first region having the filling portion. Preferably it is.

According to the present invention, the temperature of the evaporation chamber is always kept at a lower temperature than the guide portion that guides the vapor of the organic material to the film-forming material such as the substrate. In addition to the evaporation chamber, the occurrence of a cold spot having a temperature lower than that of the vapor deposition chamber is suppressed, and an organic material can be deposited with a small heat load. As a result, an organic material having a stable composition can be deposited on the film forming material without degrading the purity of the organic material and without further decomposing the organic material.
In particular, since the heat load can be reduced, an organic material having low heat resistance can be deposited while maintaining a stable composition, and an organic thin film with high purity can be obtained.

Moreover, the temperature of a filling part can be made relatively low by providing a heat radiating member in at least a bottom part among the bottom part and side surface of an evaporation part.
In addition, when the heat dissipating member is fixed by screwing, since the vapor deposition is performed in a vacuum atmosphere, the temperature variation is noticeable depending on the grounding condition. However, by directly connecting the heat dissipating member, the filling portion can be stabilized and the temperature can be relatively lowered. As described above, an organic material having a stable composition can be deposited with a simple heating mechanism without complicated control of the deposition.

It is a schematic diagram which shows an example of the vapor deposition apparatus of the organic material of the 1st Embodiment of this invention. It is a schematic diagram which shows the modification of the vapor deposition apparatus of the organic material of 1st Embodiment shown in FIG. It is typical sectional drawing which shows an example of the photoelectric conversion element formed by forming an organic thin film into a film using the vapor deposition apparatus of the organic material of 1st Embodiment shown in FIG. (A)-(c) is typical sectional drawing which shows a part of manufacturing process of the organic thin film of the photoelectric conversion element using the vapor deposition apparatus of the organic material of 1st Embodiment shown in FIG. 1 in order of a process. It is a schematic diagram which shows the principal part of the vapor deposition apparatus of the organic material of the 2nd Embodiment of this invention.

Hereinafter, an organic material vapor deposition apparatus according to the present invention will be described in detail based on preferred embodiments shown in the accompanying drawings.
FIG. 1 is a schematic view showing an example of an organic material vapor deposition apparatus according to the first embodiment of the present invention.
An organic material vapor deposition apparatus 10 shown in FIG. 1 is used for forming an organic film such as an organic EL and an organic CMOS, and deposits an organic material on a film formation material in a vacuum atmosphere. The film forming material is, for example, the substrate 100, but is not limited thereto, and examples of the film forming material include materials in the process of manufacturing an organic EL or organic CMOS.

The vapor deposition apparatus 10 basically includes a vacuum vessel 12, a vacuum exhaust unit 14 that depressurizes the inside 12 a of the vacuum vessel 12 to obtain a predetermined degree of vacuum (pressure), and a control unit that controls each unit of the vapor deposition device 10. 16. In the vapor deposition apparatus 10, even when the illustration is omitted, the control unit 16 is connected to each unit and is controlled by the control unit 16.

The vacuum exhaust unit 14 is connected to the vacuum vessel 12 via a pipe 15 and exhausts the interior 12a of the vacuum vessel 12 to maintain a predetermined degree of vacuum (pressure). The evacuation unit 14 is controlled by the control unit 16.
Moreover, the vacuum exhaust part 14 has various vacuum pumps generally used for a vapor deposition apparatus, and has vacuum pumps, such as a dry pump and a turbo-molecular pump.
The vacuum vessel 12 is provided with a pressure sensor (not shown) that measures the pressure in the interior 12 a, and this pressure sensor is connected to the control unit 16. Based on the pressure obtained by the pressure sensor, the control unit 16 operates the evacuation unit 14 to a predetermined pressure.

The vapor deposition apparatus 10 includes a material supply unit 20, an evaporation chamber 40, and a vapor guide unit 60 in the interior 12 a of the vacuum container 12.
The material supply unit 20 supplies the organic material m to a material filling unit 44 described later of the evaporation chamber 40. The material supply unit 20 includes a material stock chamber 22 that stocks the organic material m, and a material supply path 24 that communicates with the material stock chamber 22. The material supply path 24 is provided with a material discharge port 24 a at the tip, and is disposed in the evaporation chamber 40 so that the material discharge port 24 a is located above the center of the material filling portion 44 of the evaporation chamber 40. ing.
The material supply unit 20 further conducts heat conduction from the material supply path 24 to the material supply path 24 to control the material supply of the organic material m from the material supply path 24 to the evaporation chamber 40 and from the heated evaporation chamber 40 side. A heat insulating pipe 28 for blocking and a heating valve 30 for preventing the vapor Vo of the organic material m from entering the material stock chamber 22 from the material discharge port 24a are provided. The heat insulating tube 28 is made of, for example, ceramics. The heat insulating pipe 28 does not block the material supply path 24, and is always in a state in which the organic material m can move.

The supply valve 26 and the heating valve 30 are, for example, slid in the horizontal direction (left-right direction on the paper surface), thereby blocking or releasing the material supply path 24 to supply the organic material m to the evaporation chamber 40. Adjust.
A slide mechanism (not shown) for sliding the supply valve 26 and the heating valve 30 in the horizontal direction is provided. This slide mechanism is connected to the control unit 16, and the control unit 16 slides the supply valve 26 and the heating valve 30 in the horizontal direction.
In the present embodiment, the material supply path 24 is blocked by inserting the supply valve 26 and the heating valve 30 into the material supply path 24, and the material supply path 24 is released by pulling out.

The material supply unit 20 drops and supplies the organic material m to the material filling unit 44 of the evaporation chamber 40 by sliding and releasing the heating valve 30 and the supply valve 26 in the horizontal direction by a slide mechanism. After a certain amount of the organic material m is supplied, the supply valve 26 and the heating valve 30 are slid in a direction to be shut off by the slide mechanism, and the dropping of the organic material m is stopped.

The evaporation chamber 40 heats and evaporates the organic material m, and moves the generated vapor Vo to the vapor guide unit 60. The evaporation chamber 40 includes a housing 42, a material filling unit 44, an induction heating coil 48, and a high frequency power supply 50 connected to the induction heating coil 48. The high-frequency power source 50 is used for heating the organic material m, and various types generally used for induction heating can be used.

The housing 42 is made of, for example, a hollow cylindrical member. A material filling portion 44 is detachably provided on the bottom portion of the housing 42 by various methods such as screwing or engagement. Note that the material filling portion 44 may be integrated with the housing 42.
A transport pipe 62 (described later) of the steam guide unit 60 is connected to the side surface 42 a of the housing 42, and the vapor Vo of the organic material m generated in the material filling unit 44 moves to the transport pipe 62.

The material filling unit 44 functions as an evaporating dish and has a recess in which the organic material m is disposed.
In the material filling portion 44, for example, four heat radiating members 46 are directly provided on the bottom surface 44a, and two heat radiating members 46 are directly provided on the side surface 44b. None of the heat radiating members 46 are in contact with the vacuum vessel 12.
The heat radiating member 46 is constituted by, for example, a hollow cylindrical member. However, the configuration of the heat radiating member 46 is not limited to the hollow cylindrical member, and may be a truncated cone-shaped hollow member whose diameter decreases toward the tip, or a trumpet-shaped hollow member whose diameter increases toward the tip. Good. Moreover, the heat radiating member 46 is not limited to a hollow cylinder, and may be other shapes, for example, a polygon such as a hollow triangle or a hollow quadrilateral as long as it is hollow. In addition, a heat radiating fin can also be used as the heat radiating member 46.

The heat radiating member 46 is directly provided in the material filling portion 44. The direct provision means that direct connection is made by, for example, welding or brazing without using a member such as a screw or a pin. When the heat dissipating member 46 is fixed by screwing, heat is conducted to the screw due to the grounding condition, etc., heat dissipating from the heat dissipating member 46 may not be stable, and the heat dissipating function may not be sufficiently exhibited. For this reason, it is preferable that the heat dissipation member 46 is directly connected to the material filling portion 44 by welding or the like.

The heat dissipation member 46 is not limited to being provided on both the bottom surface 44a and the side surface 44b. For example, as shown in FIG. 2, four heat dissipating members 46 may be directly connected to the bottom surface 44 a as long as it is provided on either the bottom surface 44 a or the side surface 44 b.

In the evaporation chamber 40, as shown in FIG. 1, an induction heating coil 48 is disposed so as to surround the casing 42 and the material filling portion 44, and is connected to a high frequency power supply 50. The high frequency power supply 50 is connected to the control unit 16, and the control unit 16 controls the temperatures of the housing 42 and the material filling unit 44.
In the present embodiment, an induction heating method is used in which when a high frequency is applied from the high frequency power supply 50 to the induction heating coil 48, the casing 42 and the material filling portion 44 generate heat by electromagnetic induction. For this reason, as compared with the resistance heating method, the evaporation chamber 40 can be rapidly heated and lowered.

In the evaporation chamber 40, the lower part (first region) where the material filling part 44 is present and the upper part (second region) where the material filling part 44 is absent by the casing 42 are separately heated, and the respective temperatures are controlled by the control part. 16 may be controlled.
Further, the induction heating coil 48 has a high temperature when the pitch is narrowed, and conversely, the temperature is low when the pitch is widened. Therefore, the induction heating coil 48 of the pitch P ₂ of the induction heating coil 48 at the top with no material filling unit 44 by the housing 42 (second region), the lower with the material filled portion 44 (first region) By making it narrower than the pitch P ₁ , that is, by setting P ₂ <P ₁ with respect to the pitch, the upper part can always be at a higher temperature than the lower part. Thereby, a temperature difference can be produced between the upper part and the lower part without separately controlling the temperatures of the upper part and the lower part.

In the present embodiment, since the induction heating method is used, the housing 42 and the material filling portion 44 need to be configured with electromagnetic induction, and are configured with, for example, stainless steel, titanium, or graphite. Moreover, since it is necessary to connect the heat radiating member 46 to the material filling part 44 by welding or the like, it is preferable to use stainless steel, titanium or the like for the housing 42 and the material filling part 44.

The vapor guide unit 60 guides the vapor Vo generated in the material filling unit 44 to the substrate 100, and is heated and held at a temperature at which the vapor Vo state can be maintained during vapor deposition.
The steam guide section 60 includes a transport pipe 62, a discharge section 64, a heating resistor 66 for heating the transport pipe 62 and the discharge section 64, and a power supply section 68 connected to the heating resistor 66. The power supply unit 68 is connected to the control unit 16. As the power source unit 68, a general unit used for resistance heating can be appropriately used.
The substrate 100 is disposed with the surface 100a facing the ejection surface 64a of the ejection unit 64. The substrate 100 is not particularly limited as long as it is used for forming an organic thin film. For example, a silicon substrate and a glass substrate are used.
In the vapor deposition apparatus 10, the vapor Vo of the organic material m evaporated in the material filling portion 44 of the evaporation chamber 40 extends from the material filling portion 44 to the housing 42, the transport pipe 62 and the discharge portion 64 of the vapor guide portion 60. The path is called a vapor deposition path.

The transport pipe 62 guides the vapor Vo of the organic material m generated in the evaporation chamber 40 to the discharge part 64, and is made of, for example, a tubular member.
The discharge part 64 guides the vapor Vo of the organic material m to the surface 100a of the substrate 100, and is made of, for example, a tubular member. Moreover, the discharge part 64 has a plurality of openings 64b formed on the discharge surface 64a, and has a configuration like a shower head. The vapor Vo of the organic material m is emitted from the plurality of openings 64b, and an organic thin film is formed on the surface 100a of the substrate 100.

The heating resistor 66 is disposed so as to surround the steam guide portion 60 (the transport pipe 62 and the discharge portion 64), and is composed of, for example, various wires used for resistance heating.
The heating method of the steam guide unit 60 is that when a current is applied to the heating resistor 66 from the power supply unit 68, the heating resistor 66 generates heat, and the steam guide unit 60 (the transport pipe 62 and the discharge unit 64) is heated to a predetermined temperature. This is a resistance heating method that heats the material. The control unit 16 adjusts the amount of current applied from the power supply unit 68 to the heating resistor 66 to control the temperature of the steam guide unit 60 (the transport pipe 62 and the discharge unit 64).
The heating method of the steam guide unit 60 is not limited to the resistance heating method, and may be a dielectric heating method using an induction heating coil. Further, the transport pipe 62 and the discharge unit 64 may be heated separately, and the respective temperatures may be controlled by the control unit 16.

The transport pipe 62 and the discharge part 64 can be made of the same material as the housing 42 and the material filling part 44. However, since the transport pipe 62 and the discharge part 64 do not have to be a dielectric heating method, the material is not particularly limited as long as it can withstand the temperature at which the organic material m can be maintained in the state of the vapor Vo. .

In the vapor deposition apparatus 10, it is preferable to increase the temperature as the substrate 100 is closer in the order of the material filling unit 44, the casing 42, the transport pipe 62, and the discharge unit 64 during vapor deposition. That is, it is preferable to have a temperature gradient in which the temperature sequentially increases in the vapor deposition path from the evaporation of the organic material m to the arrival of the substrate 100. Thereby, generation | occurrence | production of the cold spot in a vapor deposition path | route can be suppressed further. For this reason, it is preferable that the steam guide part 60 is heated and held at a temperature higher than that of the material filling part 44.

Hereinafter, the vapor deposition method of the vapor deposition apparatus 10 will be described.
In the present embodiment, the powdery organic material m is supplied to the material stock chamber 22 of the material supply unit 20. At this time, the organic material m is blocked in the material supply path 24 by the supply valve 26 and the heating valve 30.
Next, the inside 12a of the vacuum vessel 12 is depressurized to a predetermined pressure by the vacuum exhaust part 14, and the inside 12a of the vacuum vessel 12 is made into a vacuum atmosphere.
Next, the supply valve 26 and the heating valve 30 are slid to supply a predetermined amount of the organic material m to the material filling unit 44.

Next, the evaporation chamber 40 is heated using the high-frequency power source 50, and the vapor guide unit 60 is heated using the power source unit 68 to a temperature at which the organic material m can be deposited, and is controlled by the control unit 16 so as to maintain the temperature.
At this time, the steam guide portion 60 is heated and held at a temperature higher than that of the housing 42 because the steam Vo passes therethrough. In addition, although the material filling unit 44 is heated to a temperature at which the organic material m can be deposited, since the heat is radiated by the heat radiating member 46, the temperature of the material filling unit 44 is always lower than that of the housing 42 and the steam guide unit 60. . At this time, as described above, the temperature is preferably increased as the material is closer to the substrate 100 in the order of the material filling unit 44, the casing 42, the transport pipe 62, and the discharge unit 64.
Then, the organic material m is evaporated, and the vapor Vo reaches the surface 100a of the substrate 100 through the evaporation chamber 40 and the discharge part 64, and an organic thin film is formed.

In the vapor deposition apparatus 10 of the present embodiment, the inside of the vacuum vessel 12 is depressurized to a predetermined pressure by the vacuum exhaust unit 14 and then the evaporation chamber 40 is subjected to induction heating using the high frequency power source 50 when the organic material m is vapor deposited. When the vapor guide section 60 is heated to a temperature at which the organic material m can be deposited by resistance heating using the power supply section 68 and the temperature is maintained, the material filling section 44 of the evaporation chamber 40 can be placed anywhere in the vacuum container 12 or the like. The heat is radiated by the heat radiating member 46 that is not in contact, the temperature is relatively lowest, and vapor deposition is performed in a state where the occurrence of cold spots in other vapor deposition paths is suppressed. Therefore, the vapor Vo comes into contact with various places until the vapor Vo of the organic material m passes from the material filling portion 44 through the housing 42 and the evaporation chamber 40 and exits from the discharge portion 64 of the vapor guide portion 60. However, it does not cool and temporarily adheres as an organic substance, and the organic material m is not overheated. Thereby, the organic material m can be vapor-deposited with a stable composition, and an organic thin film can be formed on the surface 100 a of the substrate 100.
Furthermore, since the occurrence of cold spots is suppressed, thermal overload on the organic material is suppressed, deterioration of the organic material can be suppressed, and the organic material is not decomposed. For this reason, even when an organic material having a low melting point is used, vapor deposition can be performed as described above.

In this embodiment, when the organic material m is deposited, the temperature of the material filling unit 44 is always lower than that of the housing 42 and the steam guide unit 60. However, even when the temperature is lowered, the temperature of the material filling unit 44 is always low. Kept.
In addition, since the dielectric heating method is used for heating the evaporation chamber 40, the time required for heating can be shortened, and when the heating is stopped, the temperature quickly decreases. Thereby, after the organic material m supplied to the evaporation chamber 40 is consumed, the time required for supplying the organic material m to the evaporation chamber 40 again can be shortened.

Hereinafter, the organic material used in the vapor deposition apparatus of the present embodiment will be specifically described by taking the produced photoelectric conversion element as an example.
FIG. 3 is a schematic cross-sectional view showing an example of a photoelectric conversion element formed by forming an organic thin film using the organic material vapor deposition apparatus of the first embodiment shown in FIG.

First, the photoelectric conversion element will be described.
A photoelectric conversion element 110 shown in FIG. 3 converts a visible light image into an electric signal, and is formed on an insulating layer 114 formed on a substrate 112.
The photoelectric conversion element 110 includes a pixel electrode (lower electrode) 116, an organic layer 118, a counter electrode (upper electrode) 120, a protective film (sealing layer) 122, a color filter 126, a partition wall 128, and a light shielding layer. 129 and an overcoat layer 130.

A reading circuit 140 and a counter electrode voltage supply unit 142 are formed on the substrate 112. As the substrate 112, for example, a glass substrate or a semiconductor substrate such as Si is used.
A plurality of pixel electrodes 116 are formed on the surface of the insulating layer 114. The pixel electrodes 116 are arranged in a one-dimensional or two-dimensional manner, for example.
In addition, a first connection portion 144 that connects the pixel electrode 116 and the readout circuit 140 is formed in the insulating layer 114. Furthermore, a second connection portion 146 that connects the counter electrode 120 and the counter electrode voltage supply unit 142 is formed. The second connection portion 146 is formed at a position not connected to the pixel electrode 116 and the organic layer 118. The first connection portion 144 and the second connection portion 146 are made of a conductive material.

A wiring layer 148 made of a conductive material for connecting the readout circuit 140 and the counter electrode voltage supply unit 142 to, for example, the outside of the photoelectric conversion element 110 is formed inside the insulating layer 114.
As described above, the insulating layer 114 formed on the substrate 112 is collectively referred to as a circuit substrate 111. The circuit board 111 is also referred to as a CMOS substrate.

An organic layer 118 is formed so as to cover the plurality of pixel electrodes 116 and to avoid the second connection portion 146. The organic layer 118 includes an electron blocking layer 150 and a photoelectric conversion layer 152.
In the organic layer 118, the electron blocking layer 150 is formed on the pixel electrode 116 side, and the photoelectric conversion layer 152 is formed on the electron blocking layer 150.
The electron blocking layer 150 is a layer for suppressing injection of electrons from the pixel electrode 116 to the photoelectric conversion layer 152.
The photoelectric conversion layer 152 generates an electric charge according to the amount of received light such as incident light L (visible light), and includes an organic photoelectric conversion material.

The counter electrode 120 is an electrode facing the pixel electrode 116 and is provided so as to cover the photoelectric conversion layer 152. A photoelectric conversion layer 152 is provided between the pixel electrode 116 and the counter electrode 120.
The counter electrode 120 is made of a conductive material that is transparent to incident light (visible light) in order to make light incident on the photoelectric conversion layer 152. The counter electrode 120 is electrically connected to the second connection portion 146 disposed outside the photoelectric conversion layer 152, and is connected to the counter electrode voltage supply portion 142 via the second connection portion 146. Yes.

The counter electrode voltage supply unit 142 applies a predetermined voltage to the counter electrode 120 via the second connection unit 146. When the voltage to be applied to the counter electrode 120 is higher than the power supply voltage of the photoelectric conversion element 110, the power supply voltage is boosted by a booster circuit such as a charge pump to supply the predetermined voltage.

The pixel electrode 116 is an electrode for collecting electric charges for collecting electric charges generated in the organic layer 118 (photoelectric conversion layer 152). The pixel electrode 116 is connected to the readout circuit 140 through the first connection portion 144. The readout circuit 140 is provided on the substrate 112 corresponding to each of the plurality of pixel electrodes 116, and reads out a signal corresponding to the charge collected by the corresponding pixel electrode 116.

The reading circuit 140 is constituted by, for example, a CCD, a MOS circuit, a TFT circuit, or the like, and is shielded from light by a light shielding layer (not shown) provided in the insulating layer 114.
Although not shown, for example, a high-concentration n region surrounded by a p region is formed on the substrate 112, and the first connection portion 144 is connected to the n region. A read circuit 140 is provided in the p region. The n region functions as a charge accumulation unit that accumulates charges of the photoelectric conversion layer 152. The signal charge accumulated in the n region is converted into a signal corresponding to the amount of charge by the readout circuit 140 and output to the outside of the photoelectric conversion element 110 via the wiring layer 148, for example.

The protective film 122 is for protecting the organic layer 118 including the photoelectric conversion layer 152 from deterioration factors such as water molecules and oxygen. The protective film 122 is formed so as to cover the counter electrode 120, and is formed of, for example, a silicon oxynitride film (SiON film). Further, the incident light L (visible light) reaches the organic layer 118 through the protective film 122. Therefore, the protective film 122 is transparent to light having a wavelength detected by the organic layer 118, for example, visible light.

The color filter 126 is formed at a position facing each pixel electrode 116 on the protective film 122. The partition wall 128 is provided between the color filters 126 on the protective film 122 and is for improving the light transmission efficiency of the color filter 126. The light shielding layer 129 is formed in a region other than the region (effective pixel region) provided with the color filter 126 and the partition wall 128 on the protective film 122, and light is incident on the photoelectric conversion layer 152 formed outside the effective pixel region. Is to prevent. The color filter 126, the partition wall 128, and the light shielding layer 129 are formed by, for example, a photolithography method.

The overcoat layer 130 is for protecting the color filter 126 from subsequent processes and is formed so as to cover the color filter 126, the partition wall 128 and the light shielding layer 129.
In the photoelectric conversion element 110, one pixel electrode 116, in which the organic layer 118, the counter electrode 120, and the color filter 126 are provided above, is a unit pixel.

As the overcoat layer 130, a known layer used for an organic solid-state image sensor is used. For the overcoat layer 130, a polymer material such as an acrylic resin, a polysiloxane resin, a polystyrene resin, or a fluorine resin, or an inorganic material such as silicon oxide or silicon nitride can be used as appropriate. The overcoat layer 130 may be formed in a predetermined vacuum or non-vacuum. Note that the overcoat layer 130 can be used as an antireflection layer, and it is also preferable to form various low refractive index materials used as the partition walls of the color filter 126.

The counter electrode 120 and the pixel electrode 116 are made of a conductive material. As the conductive material, a metal, an alloy, a metal oxide, an electrically conductive compound, a mixture thereof, or the like can be used. Since light enters from the counter electrode 120, the counter electrode 120 needs to be sufficiently transparent to the light to be detected. Specific examples of the counter electrode 120 include tin oxide (ATO, FTO) doped with antimony or fluorine, tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO). Conductive metal oxides, metal thin films such as gold, silver, chromium, nickel, and mixtures or laminates of these metals and conductive metal oxides, inorganic conductive materials such as copper iodide and copper sulfide, polyaniline, Examples thereof include organic conductive materials such as polythiophene and polypyrrole, and laminates of these with ITO.

Depending on the application, the pixel electrode 116 may have transparency, or conversely, may use a material that does not have transparency and reflects light. Specifically, the pixel electrode 116 is made of tin oxide (ATO, FTO) doped with antimony or fluorine, tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), or the like. Conductive metal oxides, metals such as gold, silver, chromium, nickel, titanium, tungsten, and aluminum, and conductive compounds such as oxides and nitrides of these metals, and also between these metals and conductive metal oxides Examples thereof include mixtures or laminates, inorganic conductive substances such as copper iodide and copper sulfide, organic conductive materials such as polyaniline, polythiophene and polypyrrole, and laminates of these with ITO.
Note that a method for forming the electrode is not particularly limited, and can be appropriately selected in consideration of appropriateness with the electrode material described above.

The electron blocking layer 150 preferably contains a compound represented by the following general formula (I).

In general formula (F-1), R ₁₁ to R ₁₈ and R ′ ₁₁ to R ′ ₁₈ are each independently a hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, hydroxyl group, amino group, or mercapto. Represents a group, and these may further have a substituent. _However, any one in R 15 _{~ R 18} is linked to any one in R _'15 ~ R' _18, to form a single bond. A ₁₁ and A ₁₂ each independently represent a substituent represented by the following general formula (A-1), and any one of R ₁₁ to R ₁₄ and any of R ′ ₁₁ to R ′ ₁₄ Replace as one. Y independently represents a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, or a silicon atom, and these may further have a substituent.

In general formula (A-1), Ra ₁ to Ra ₈ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, and these may further have a substituent. . At least two members out of Ra ₁ to Ra ₈ may be bonded to each other to form a ring. * Represents a bonding position. Xa represents a single bond, an oxygen atom, a sulfur atom, an alkylene group, a silylene group, an alkenylene group, a cycloalkylene group, a cycloalkenylene group, an arylene group, a divalent heterocyclic group, or an imino group, and these further represent a substituent. You may have. S ₁₁ independently represents the following substituent (S ₁₁ ) and is substituted as any one of Ra ₁ to Ra ₈ . Each n independently represents an integer of 1 to 4.

R ₁ to R ₃ each independently represents a hydrogen atom or an alkyl group. At least two of R ₁ to R ₃ may be bonded to each other to form a ring.

The electron blocking layer 150 uses an organic compound (organic material) represented by the general formula (I) as an electron blocking material. In addition, the compound 1 shown below is a specific example of the said general formula (I), and this compound 1 is a powder.

As the electron blocking layer 150, in addition to the above, for example, an electron blocking material of Compound 2 shown below can be used. This compound 2 is a powder.

The thickness of the electron blocking layer 150 is preferably 10 nm to 300 nm, more preferably 30 nm to 150 nm, and particularly preferably 50 nm to 100 nm. By setting the thickness of the electron blocking layer 150 to 10 nm or more, a suitable dark current suppressing effect can be obtained, and by setting the thickness of the electron blocking layer 150 to 300 nm or less, preferable photoelectric conversion efficiency can be obtained.

The organic material constituting the photoelectric conversion layer 152 preferably contains at least one of p-type organic semiconductor and n-type organic semiconductor. Hereinafter, the p-type organic semiconductor and the n-type organic semiconductor will be described.

The p-type organic semiconductor (compound) is a donor organic semiconductor (compound), which is mainly represented by a hole-transporting organic compound and refers to an organic compound having a property of easily donating electrons. More specifically, an organic compound having a smaller ionization potential when two organic materials are used in contact with each other. Therefore, any organic compound can be used as the donor organic compound as long as it is an electron-donating organic compound. For example, triarylamine compound, benzidine compound, pyrazoline compound, styrylamine compound, hydrazone compound, triphenylmethane compound, carbazole compound, polysilane compound, thiophene compound, phthalocyanine compound, cyanine compound, merocyanine compound, oxonol compound, polyamine compound, indole Compounds, pyrrole compounds, pyrazole compounds, polyarylene compounds, condensed aromatic carbocyclic compounds (naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, fluoranthene derivatives), nitrogen-containing heterocyclic compounds The metal complex etc. which it has as can be used. Not limited to this, as described above, any organic compound having an ionization potential smaller than that of the organic compound used as the n-type (acceptor property) compound may be used as the donor organic semiconductor.

Among the above, a triarylamine compound is preferable. Among these, triarylamine compounds represented by the following general formula (II) are more preferable.

In the general formula (II), Z ₁ is a ring containing at least two carbon atoms and represents a 5-membered ring, a 6-membered ring, or a condensed ring containing at least one of a 5-membered ring and a 6-membered ring. L ₁ , L ₂ and L ₃ each represents an unsubstituted methine group or a substituted methine group. D ₁ represents an atomic group having a hetero atom. n ₁ represents an integer of 0 or more.

Z ₁ is a ring containing at least two carbon atoms, and represents a 5-membered ring, a 6-membered ring, or a condensed ring containing at least one of a 5-membered ring and a 6-membered ring. As the condensed ring containing at least one of a 5-membered ring, a 6-membered ring, and a 5-membered ring and a 6-membered ring, those usually used as an acidic nucleus in a merocyanine dye are preferable. Specific examples thereof include the following: Can be mentioned.

(A) 1,3-dicarbonyl nucleus: for example, 1,3-indandione nucleus, 1,3-cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione, 1,3-dioxane-4,6 -Dione etc.
(B) pyrazolinone nucleus: for example, 1-phenyl-2-pyrazolin-5-one, 3-methyl-1-phenyl-2-pyrazolin-5-one, 1- (2-benzothiazoyl) -3-methyl- 2-pyrazolin-5-one and the like.
(C) isoxazolinone nucleus: for example, 3-phenyl-2-isoxazolin-5-one, 3-methyl-2-isoxazolin-5-one, etc.
(D) Oxindole nucleus: For example, 1-alkyl-2,3-dihydro-2-oxindole and the like.
(E) 2,4,6-triketohexahydropyrimidine nucleus: for example, barbituric acid or 2-thiobarbituric acid and derivatives thereof. Examples of the derivatives include 1-alkyl compounds such as 1-methyl and 1-ethyl, 1,3-dialkyl compounds such as 1,3-dimethyl, 1,3-diethyl and 1,3-dibutyl, and 1,3-diphenyl. 1,3-diaryl compounds such as 1,3-di (p-chlorophenyl) and 1,3-di (p-ethoxycarbonylphenyl), and 1-alkyl-1-aryl compounds such as 1-ethyl-3-phenyl 1,3-di (2-pyridyl) 1,3-diheterocyclic substituents and the like.
(F) 2-thio-2,4-thiazolidinedione nucleus: for example, rhodanine and derivatives thereof. Examples of the derivatives include 3-alkylrhodanine such as 3-methylrhodanine, 3-ethylrhodanine and 3-arylrhodanine, 3-arylrhodanine such as 3-phenylrhodanine, and 3- (2-pyridyl). And 3-position heterocyclic-substituted rhodanine such as rhodanine.

(G) 2-thio-2,4-oxazolidinedione (2-thio-2,4- (3H, 5H) -oxazoledione nucleus: for example, 3-ethyl-2-thio-2,4-oxazolidinedione and the like.
(H) Tianaphthenone nucleus: For example, 3 (2H) -thianaphthenone-1,1-dioxide and the like.
(I) 2-thio-2,5-thiazolidinedione nucleus: for example, 3-ethyl-2-thio-2,5-thiazolidinedione and the like.
(J) 2,4-thiazolidinedione nucleus: for example, 2,4-thiazolidinedione, 3-ethyl-2,4-thiazolidinedione, 3-phenyl-2,4-thiazolidinedione and the like.
(K) Thiazolin-4-one nucleus: for example, 4-thiazolinone, 2-ethyl-4-thiazolinone, etc.
(L) 2,4-imidazolidinedione (hydantoin) nucleus: for example, 2,4-imidazolidinedione, 3-ethyl-2,4-imidazolidinedione, etc.
(M) 2-thio-2,4-imidazolidinedione (2-thiohydantoin) nucleus: for example, 2-thio-2,4-imidazolidinedione, 3-ethyl-2-thio-2,4-imidazolidine Zeon etc.
(N) Imidazolin-5-one nucleus: For example, 2-propylmercapto-2-imidazolin-5-one and the like.
(O) 3,5-pyrazolidinedione nucleus: for example, 1,2-diphenyl-3,5-pyrazolidinedione, 1,2-dimethyl-3,5-pyrazolidinedione, etc.
(P) Benzothiophen-3-one nucleus: for example, benzothiophen-3-one, oxobenzothiophen-3-one, dioxobenzothiophen-3-one and the like.
(Q) Indanone nucleus: for example, 1-indanone, 3-phenyl-1-indanone, 3-methyl-1-indanone, 3,3-diphenyl-1-indanone, 3,3-dimethyl-1-indanone, etc.

The ring represented by Z ₁ is preferably a 1,3-dicarbonyl nucleus, a pyrazolinone nucleus, a 2,4,6-triketohexahydropyrimidine nucleus (including a thioketone body, for example, a barbituric acid nucleus, 2-thio Barbituric acid nucleus), 2-thio-2,4-thiazolidinedione nucleus, 2-thio-2,4-oxazolidinedione nucleus, 2-thio-2,5-thiazolidinedione nucleus, 2,4-thiazolidinedione nucleus, 2,4-imidazolidinedione nucleus, 2-thio-2,4-imidazolidinedione nucleus, 2-imidazolin-5-one nucleus, 3,5-pyrazolidinedione nucleus, benzothiophen-3-one nucleus, indanone A nucleus, more preferably a 1,3-dicarbonyl nucleus, a 2,4,6-triketohexahydropyrimidine nucleus (including a thioketone body, for example, a barbituric acid nucleus, Obarbituric acid nucleus), 3,5-pyrazolidinedione nucleus, benzothiophen-3-one nucleus, indanone nucleus, more preferably 1,3-dicarbonyl nucleus, 2,4,6-triketohexahydropyrimidine Nuclei (including thioketone bodies, for example, barbituric acid nuclei, 2-thiobarbituric acid nuclei), particularly preferably 1,3-indandione nuclei, barbituric acid nuclei, 2-thiobarbituric acid nuclei and their Is a derivative of

What is preferable as a ring represented by Z ₁ is represented by the following formula.

Z ³ represents a ring containing at least 3 carbon atoms, and represents a 5-membered ring, a 6-membered ring, or a condensed ring containing at least one of a 5-membered ring and a 6-membered ring. Z ³ can be selected from the ring formed by Z ₁ and is preferably a 1,3-dicarbonyl nucleus, a 2,4,6-triketohexahydropyrimidine nucleus (including a thioketone body), Particularly preferred are 1,3-indandione nucleus, barbituric acid nucleus, 2-thiobarbituric acid nucleus and derivatives thereof.

In the compound represented by the general formula (II), the structure represented by D ₁ functions as a donor part and the structure represented by Z ₁ as an acceptor part, and both are linked via L ₁ or the like. It has been found useful as a conversion material.
Further, when used in combination with n-type semiconductor material, such as C ₆₀ (acceptor), by controlling the interaction between acceptor parts, when used as a co-deposited film with C _60, to express the high hole-transporting property It was found that things could be done.
Here, the structure of the acceptor part and the interaction can be controlled by introducing a substituent that causes steric hindrance. In the barbituric acid nucleus and 2-thiobarbituric acid nucleus, it is possible to control the interaction between molecules preferably by substituting two hydrogen atoms at two N positions with a substituent. Examples of the substituent W include those described below, more preferably an alkyl group, and still more preferably a methyl group, an ethyl group, a propyl group, or a butyl group.
When the ring represented by Z ₁ is a 1,3-indandione nucleus, it is preferably a group represented by the following general formula (IV) or a group represented by the following general formula (V).

R ₄₁ to R ₄₄ each independently represents a hydrogen atom or a substituent.

R ₄₁ , R ₄₄ and R ₄₅ to R ₄₈ each independently represent a hydrogen atom or a substituent.
In the case of the group represented by the general formula (IV), R ₄₁ to R ₄₄ each independently represents a hydrogen atom or a substituent. As the substituent, for example, those mentioned as the substituent W can be applied. R ₄₁ to R ₄₄ are adjacent to each other and can be bonded to form a ring (the ring to be formed includes ring R described later), and R ₄₂ and R ₄₃ are bonded to each other. It is preferable to form a ring (for example, a benzene ring, a pyridine ring, a pyrazine ring). R ₄₁ to R ₄₄ are preferably all hydrogen atoms.
The case where the group represented by the general formula (IV) is a group represented by the general formula (V) is preferable.
In the case of the group represented by the general formula (V), R ₄₁ , R ₄₄ , R ₄₅ to R ₄₈ each independently represents a hydrogen atom or a substituent. As the substituent, for example, those mentioned as the substituent W can be applied. R ₄₁ , R ₄₄ and R ₄₅ to R ₄₈ are preferably all hydrogen atoms.

When the ring represented by Z ₁ is a 2,4,6-triketohexahydropyrimidine nucleus (including a thioketone form), it is preferably a group represented by the following general formula (VI). The following R ₈₁ and R ₈₂ each independently represent a hydrogen atom or a substituent. R ₈₃ represents an oxygen atom, a sulfur atom or a substituent.

In the case of the group represented by the general formula (VI), R ₈₁ and R ₈₂ each independently represents a hydrogen atom or a substituent. As the substituent, for example, those mentioned as the substituent W can be applied. R ₈₁ and R ₈₂ are each independently preferably an alkyl group, an aryl group or a heterocyclic group (such as 2-pyridyl), and an alkyl group having 1 to 6 carbon atoms (eg, methyl, ethyl, n-propyl, t-). (Butyl) is more preferable.
R ₈₃ represents an oxygen atom, a sulfur atom or a substituent, and R ₈₃ preferably represents an oxygen atom or a sulfur atom. As the substituent, those in which the bond is a nitrogen atom and those having a carbon atom are preferable. In the case of a nitrogen atom, an alkyl group (having 1 to 12 carbon atoms) or an aryl group (having 6 to 12 carbon atoms) is preferable. Specific examples include a methylamino group, an ethylamino group, a butylamino group, a hexylamino group, a phenylamino group, and a naphthylamino group. In the case of a carbon atom, it is sufficient that at least one electron-withdrawing group is substituted. Examples of the electron-withdrawing group include a carbonyl group, a cyano group, a sulfoxide group, a sulfonyl group, and a phosphoryl group. It is good to have. Examples of this substituent include W. R ₈₃ is preferably one that forms a 5-membered or 6-membered ring containing a carbon atom at the bond, and specifically includes those having the following structures.

Ph in the above group represents a phenyl group.
In the general formula (II), L ₁ , L ₂ and L ₃ each independently represents an unsubstituted methine group or a substituted methine group. The substituted methine groups may be bonded to each other to form a ring (eg, a 6-membered ring such as a benzene ring). Although the substituent of the substituted methine group includes the substituent W, it is preferable that all of L ₁ , L ₂ and L ₃ are unsubstituted methine groups.

In the general formula (II), n represents an integer of 0 or more, preferably 0 or more and 3 or less, and more preferably 0. When n is increased, the absorption wavelength region can be made longer, or the thermal decomposition temperature is lowered. N = 0 is preferable in that it has appropriate absorption in the visible region and suppresses thermal decomposition during vapor deposition.

In the general formula (II), D ₁ represents an atomic group having a hetero atom.
The D ₁ is preferably a group containing —NR ^a (R ^b ), and the D ₁ may further have an aryl group substituted with —NR ^a (R ^b ) (preferably, may have a substituent). , A phenyl group or a naphthyl group) is preferable.
R ^a and R ^b each independently represent a hydrogen atom or a substituent, and examples of the substituent represented by R ^a and R ^b include the substituent W, but the substituent may preferably have a substituent. , An aliphatic hydrocarbon group (preferably an alkyl group or alkenyl group which may have a substituent), an aryl group (preferably a phenyl group which may have a substituent), or a heterocyclic group. The heterocycle is preferably a 5-membered ring such as furan, thiophene, pyrrole or oxadiazole.

When R ^a and R ^b are an aliphatic hydrocarbon group, an aryl group or a heterocyclic group, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, Aryloxycarbonyl group, acylamino group, sulfonylamino group, sulfonyl group, silyl group, aromatic heterocyclic group, more preferably alkyl group, alkenyl group, aryl group, alkoxy group, aryloxy group, silyl group, aromatic A heterocyclic group, more preferably an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a silyl group, and an aromatic heterocyclic group. As specific examples, those exemplified for the substituent W can be applied.

R ^a and R ^b are preferably an alkyl group, an aryl group, or an aromatic heterocyclic group. R ^a and R ^b are particularly preferably an alkyl group, an alkylene group linked to L to form a ring, or an aryl group, and more preferably an alkyl group having 1 to 8 carbon atoms, and L to 5 to 6 linked to L. An alkylene group forming a member ring, or a substituted or unsubstituted phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted phenyl group.

When R ^a and R ^b are a substituent (preferably an alkyl group, an alkenyl group, or a group having these groups as a substituent), these groups are those of the aryl group substituted by —NR ^a (R ^b ). A ring (preferably a 6-membered ring) may be formed by bonding to a hydrogen atom of an aromatic ring (preferably benzene ring) skeleton or a substituent. In this case, the case represented by the general formula (VIII), (IX) or (X) described later is preferable.
R ^a and R ^b are bonded to each other to form a ring (the ring to be formed includes a ring R described later, preferably a 5-membered or 6-membered ring, more preferably a 6-membered ring). R ^a and R ^b may be bonded to a substituent in L (representing any one of L ₁ , L ₂ , and L ₃ ) to form a ring (preferably a 5- or 6-membered ring, more preferably May form a 6-membered ring).
D ₁ is preferably an aryl group substituted with an amino group at the para position (preferably a phenyl group). In this case, it is preferably represented by the following general formula (IID). This amino group may be substituted. Examples of the substituent of the amino group include a substituent W, but an aliphatic hydrocarbon group (preferably an alkyl group which may have a substituent) and an aryl group (preferably may have a substituent). A phenyl group) or a heterocyclic group. The amino group is preferably a so-called diaryl group-substituted amino group in which two aryl groups are substituted. In this case, the amino group is preferably represented by the following general formula (III). Further, the substituent of this amino group (preferably an alkyl group or alkenyl group which may have a substituent) is bonded to a hydrogen atom of the aromatic ring (preferably benzene ring) skeleton of the aryl group or a substituent to form a ring. (Examples of the ring to be formed include a ring R described later, preferably a 6-membered ring).

In the formula, R ₁ to R ₆ each independently represents a hydrogen atom or a substituent. R ₁ and R ₂ , R ₃ and R ₄ , R ₅ and R ₆ , R ₂ and R ₅ , and R ₄ and R ₆ may be bonded to each other to form a ring.

In general formula (III), R ₈₁₁ to R ₈₁₄ , R ₈₂₀ to R ₈₂₄ , and R ₈₃₀ to R ₈₃₄ each independently represent a hydrogen atom or a substituent. Further, at least two of R ₈₁₁ to R ₈₁₄ , R ₈₂₀ to R ₈₂₄ , and R ₈₃₀ to R ₈₃₄ may be bonded to each other to form a ring.
It is also preferred that D ₁ is represented by the following general formula (VII).

In the formula, R ₉₁ to R ₉₈ each independently represents a hydrogen atom or a substituent. m represents an integer of 0 or more. Rx and Ry each independently represent a hydrogen atom or a substituent. When m is 2 or more, Rx and Ry bonded to each 6-membered ring may be different substituents. R ₉₁ and R ₉₂ , R ₉₂ and Rx, Rx and R ₉₄ , R ₉₄ and R ₉₇ , R ₉₃ and Ry, Ry and R ₉₅ , R ₉₅ and R ₉₆ , R ₉₇ and R ₉₈ are independent of each other. Thus, a ring may be formed. Further, the bond with L ₃ (L ₁ when n ₁ is 0) may be at the position of R ₉₁ , R ₉₂ , R ₉₃ , and in that case, the bond with L ₃ in the general formula (VII) A substituent or a hydrogen atom corresponding to R ₉₁ , R ₉₂ , or R ₉₃ may be bonded to the site represented as, and adjacent Rs may be bonded to form a ring. Here, “adjacent Rs may be bonded to form a ring” means, for example, when R ₉₁ is a bonding part with L ₃ (L ₁ when n ₁ is 0), If R ₉₀ is bonded to the bonding portion of the general formula (VII), R ₉₀ and R ₉₃ may bond to form a ring, and R ₉₂ is L ₃ (when n ₁ is 0). Is bonded to L ₁ ), and R ₉₀ is bonded to the bonded portion of the general formula (VII), R ₉₀ and R ₉₁ , and R ₉₀ and R ₉₃ are bonded to form a ring. In the case where R ₉₃ is a bonding portion with L ₃ (L ₁ when n ₁ is 0), it is assumed that R ₉₀ is bonded to the bonding portion of the general formula (VII). R ₉₀ and R ₉₁ , R ₉₁ and R ₉₂ may be bonded to each other to form a ring.

The above ring is preferably a benzene ring.
The substituent of R ₉₁ to R ₉₈ , Rx and Ry includes the substituent W.
R ₉₁ to R ₉₆ are all preferably hydrogen atoms, and Rx and Ry are preferably both hydrogen atoms. R ₉₁ to R ₉₆ are preferably hydrogen atoms, and Rx and Ry are also preferably hydrogen atoms.
R ₉₇ and R ₉₈ each independently preferably represent a phenyl group which may be substituted, and examples of the substituent include the substituent W, and an unsubstituted phenyl group is preferable. m represents an integer of 0 or more, and 0 or 1 is preferable.
It is also preferred that D ₁ is a group represented by the general formula (VIII), (IX) or (X).

In the formula, R ₅₁ to R ₅₄ each independently represent a hydrogen atom or a substituent. Substituent W is mentioned as this substituent. R ₅₂ and R ₅₃ , or R ₅₁ and R ₅₂ may be linked to form a ring.

In the formula, R ₆₁ to R ₆₄ each independently represents a hydrogen atom or a substituent. Substituent W is mentioned as this substituent. R ₆₂ and R ₆₃ , or R ₆₁ and R ₆₂ may be linked to form a ring.

In the formula, R ₇₁ to R ₇₃ each independently represents a hydrogen atom or a substituent. Substituent W is mentioned as this substituent. R ₇₂ and R ₇₃ may be linked to form a ring.

The group represented by the general formula (IID) or the general formula (III) is more preferably used as the D ₁ .

In the general formula (IID), R ₁ to R ₆ each independently represents a hydrogen atom or a substituent. R ₁ and R ₂ , R ₃ and R ₄ , R ₅ and R ₆ , R ₂ and R ₅ , and R ₄ and R ₆ may be bonded to each other to form a ring. Examples of the ring to be formed include the ring R described later.
Examples of the substituent in R ₁ to R ₄ include the substituent W, preferably R ₁ to R ₄ are a hydrogen atom, or R ₂ and R ₅ or R ₄ and R ₆ form a 5-membered ring. More preferably, all of R ₁ to R ₄ are hydrogen atoms.
The substituent in R ₅ and R ₆ includes the substituent W, and among the substituents, a substituted or unsubstituted aryl group is preferable, and the substituent of the substituted aryl group is an alkyl group (for example, a methyl group, an ethyl group, or the like). Group) and an aryl group (for example, phenyl group, naphthylene group, phenanthryl group, anthryl group) are preferable. R5 and R6 are preferably a phenyl group, an alkyl-substituted phenyl group, a phenyl-substituted phenyl group, a naphthyl group, a phenanthryl group, an anthryl group, or a fluorenyl group (preferably a 9,9′-dimethyl-2-fluorenyl group).

In general formula (III), R ₁₁ to R ₁₄ , R ₂₀ to R ₂₄ , and R ₃₀ to R ₃₄ each independently represent a hydrogen atom or a substituent. R ₁₁ to R ₁₄ , R ₂₀ to R ₂₄ , and R ₃₀ to R ₃₄ may be bonded to each other to form a ring. Examples of the ring to be formed include the ring R described later. As an example of the ring formation, R ₁₁ and R ₁₂ , R ₁₃ and R ₁₄ are bonded to form a benzene ring, and two adjacent R ₂₀ to R ₂₄ (R ₂₄ and R ₂₃ , R ₂₃ and R ₂₀ , R ₂₀ and R ₂₁ , R ₂₁ and R ₂₂ ) combine to form a benzene ring, and two adjacent R ₃₀ to R ₃₄ (R ₃₄ and R ₃₃ , R ₃₃ and R ₃₀ , R ₃₀ and R ₃₁ , R ₃₁ and R ₃₂ ) are combined to form a benzene ring, and R ₂₂ and R ₃₄ are combined to form a 5-membered ring with an N atom.
Examples of the substituent represented by R ₁₁ to R ₁₄ , R ₂₀ to R ₂₄ , and R ₃₀ to R ₃₄ include the substituent W. Preferably, the substituent is an alkyl group (for example, methyl group, ethyl group), an aryl group (for example, , Phenyl group, naphthyl group), and these groups may be further substituted with a substituent W (preferably an aryl group). In particular, R ₂₀ and R ₃₀ are preferably substituents, and the other R ₁₁ to R ₁₄ , R ₂₀ to R ₂₄ , and R ₃₀ to R ₃₄ are more preferably hydrogen atoms.

The compound represented by the general formula (II) is preferably a compound represented by the following general formula (pI).

In the general formula (pI), Z ₁ represents a ring containing at least two carbon atoms, and represents a 5-membered ring, a 6-membered ring, or a condensed ring containing at least one of a 5-membered ring and a 6-membered ring. L ₁ , L ₂ and L ₃ each independently represents an unsubstituted methine group or a substituted methine group. n ₁ represents an integer of 0 or more. Rp ₁ , Rp ₂ , Rp ₃ , Rp ₄ , Rp ₅ , Rp ₆ each independently represents a hydrogen atom or a substituent. Rp ₁ and Rp ₂ , Rp ₂ and Rp ₃ , Rp ₄ and Rp ₅ , Rp ₅ and Rp ₆ may be bonded to each other to form a ring. Rp ₂₁ and Rp ₂₂ each independently represent a substituted aryl group, an unsubstituted aryl group, a substituted heteroaryl group, or an unsubstituted heteroaryl group.

As a photoelectric conversion material, a compound having a naphthylene group as a connecting part of a donor part (site of —NRp ₂₁ Rp ₂₂ ) / acceptor part (site bonded to a naphthylene group via L ₁ to L ₃ ) as described above. By using it together with fullerenes, a photoelectric conversion element having excellent heat resistance and high-speed response can be obtained. This is considered that the interaction with the fullerenes is improved and the response speed is improved by using a naphthylene group as the connecting part of the donor part / acceptor part. Moreover, the said compound has sufficient sensitivity.

In formula _{_{_{(pI), Z 1, L}}} 1, L 2, L 3, n 1 has the same meaning as _{_{_{_{Z 1, L 1, L 2}}}} , L 3, n 1 in formula (II), a preferred range Is the same.

Rp ₁ to Rp ₆ each independently represents a hydrogen atom or a substituent. If Rp ₁ ~ Rp ₆ represents a _substituent, but the substituent represented by Rp 1 ~ Rp ₆ include the later-described substituent W, especially halogen atom, an alkyl group, an aryl group, a heterocyclic group, hydroxy group, A nitro group, alkoxy group, aryloxy group, heterocyclic oxy group, amino group, alkylthio group, arylthio group, alkenyl group, and cyano group heterocyclic thio group are preferred.
Rp ₁ to Rp ₆ are each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a hydroxy group, a nitro group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an amino group, or an alkylthio group. , An arylthio group, an alkenyl group, a cyano group or a heterocyclic thio group, more preferably a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a carbon number An aryl group having 6 to 20 carbon atoms and a heterocyclic group having 4 to 16 carbon atoms are more preferable, and a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and an aryl group having 6 to 14 carbon atoms are further preferable, and a hydrogen atom and carbon number 1 More preferred are an alkyl group of 6 to 6 and an aryl group of 6 to 10 carbon atoms, and a hydrogen atom is particularly preferred. In the case of an alkyl group, there may be a branch. Further, when Rp1 to Rp6 are substituents, they may have further substituents. Further substituents include the substituent W described below. When there are a plurality of further substituents, the plurality of substituents may be linked to form a ring. Examples of the ring formed include ring R described later.
Preferable specific examples of Rp ₁ to Rp ₆ include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, a phenyl group, and a naphthyl group.

Rp ₁ and Rp ₂ , Rp ₂ and Rp ₃ , Rp ₄ and Rp ₅ , Rp ₅ and Rp ₆ may be bonded to each other to form a ring. Examples of the ring formed include ring R described later. Preferred are a benzene ring, a naphthalene ring, an anthracene ring, a pyridine ring, a pyrimidine ring and the like.

Rp ₂₁ and Rp ₂₂ each independently represent a substituted aryl group, an unsubstituted aryl group, a substituted heteroaryl group, or an unsubstituted heteroaryl group.
It is preferable that both Rp ₂₁ and Rp ₂₂ are not unsubstituted phenyl groups.
The aryl group represented by Rp ₂₁ and Rp ₂₂ is preferably an aryl group having 6 to 30 carbon atoms, and more preferably an aryl group having 6 to 20 carbon atoms. Specific examples of the aryl group include a phenyl group, a naphthyl group, a biphenylyl group, a terphenyl group, an anthryl group, and a fluorenyl group.
Examples of the substituent of the substituted aryl group in Rp ₂₁ and Rp ₂₂ include an alkyl group (for example, methyl group, ethyl group, t-butyl group), an alkoxy group (for example, methoxy group, ethoxy group, isopropoxy group), aryl group (For example, phenyl group, naphthyl group, phenanthryl group, anthryl group) and heteroaryl groups (for example, thienyl group, furanyl group, pyridyl group, carbazolyl group) are preferable.

The aryl group or substituted aryl group represented by Rp ₂₁ or Rp ₂₂ is preferably a phenyl group, a substituted phenyl group, a biphenyl group, a naphthyl group, a phenanthryl group, an anthryl group, a fluorenyl group, or a substituted fluorenyl group (preferably 9,9 ′ -Dialkyl-2-fluorenyl group).

When Rp ₂₁ and Rp ₂₂ are heteroaryl groups, the heteroaryl group is preferably a heteroaryl group consisting of a 5-membered, 6-membered or 7-membered ring or a condensed ring thereof. Examples of the hetero atom contained in the heteroaryl group include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the ring constituting the heteroaryl group include a furan ring, a thiophene ring, a pyrrole ring, a pyrroline ring, a pyrrolidine ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, an imidazoline ring, and an imidazolidine. Ring, pyrazole ring, pyrazoline ring, pyrazolidine ring, triazole ring, furazane ring, tetrazole ring, pyran ring, thiine ring, pyridine ring, piperidine ring, oxazine ring, morpholine ring, thiazine ring, pyridazine ring, pyrimidine ring, pyrazine ring, Examples include a piperazine ring and a triazine ring.
As the condensed ring, benzofuran ring, isobenzofuran ring, benzothiophene ring, indole ring, indoline ring, isoindole ring, benzoxazole ring, benzothiazole ring, indazole ring, benzimidazole ring, quinoline ring, isoquinoline ring, cinnoline ring, Phthalazine ring, quinazoline ring, quinoxaline ring, dibenzofuran ring, carbazole ring, xanthene ring, acridine ring, phenanthridine ring, phenanthroline ring, phenazine ring, phenoxazine ring, thianthrene ring, thienothiophene ring, indolizine ring, quinolidine ring, A quinuclidine ring, a naphthyridine ring, a purine ring, a pteridine ring, etc. are mentioned.

Examples of the substituent of the substituted heteroaryl group in Rp ₂₁ and Rp ₂₂ include an alkyl group (for example, methyl group, ethyl group, t-butyl group), an alkoxy group (for example, methoxy group, ethoxy group, isopropoxy group), aryl A group (for example, phenyl group, naphthyl group, phenanthryl group, anthryl group) or a heteroaryl group (for example, thienyl group, furanyl group, pyridyl group, carbazolyl group) is preferable.
The ring constituting the heteroaryl group or substituted heteroaryl group represented by Rp ₂₁ and Rp ₂₂ is preferably a thiophene ring, substituted thiophene ring, furan ring, substituted furan ring, thienothiophene ring, substituted thienothiophene ring, carbazolyl group It is.

Rp ₂₁ and Rp ₂₂ are each independently preferably a phenyl group, a naphthyl group, a fluorenyl group, a biphenyl group, an anthracenyl group, or a phenanthrenyl group, and more preferably a phenyl group, a naphthyl group, or a fluorenyl group. When Rp21 and Rp22 have a substituent, the substituent is preferably an alkyl group, a halogenated alkyl group, an alkoxy group, an aryl group or a heteroaryl group, more preferably a methyl group, an isopropyl group, a t-butyl group, A trifluoromethyl group, a phenyl group, or a carbazolyl group;

When Z ₁ is a group represented by the general formula (VI) or a group represented by the general formula (VII), the compound represented by the general formula (pI) is represented by the following general formula (pII), respectively. Or a compound represented by the following general formula (pIII).
The compound represented by the general formula (pI) is preferably a compound represented by the following general formula (pII) or a compound represented by the following general formula (pIII).

In the general formula (pII), L ₁ , L ₂ , L ₃ , n ₁ , Rp ₁ , Rp ₂ , Rp ₃ , Rp ₄ , Rp ₅ , Rp ₆ , Rp ₂₁ , Rp ₂₂ are represented by the general formula (pI) It is synonymous and the preferable range is also the same. Rp ₄₁ , Rp ₄₂ , Rp ₄₃ , Rp ₄₄ are synonymous with R ₄₁ , R ₄₂ , R ₄₃ , R ₄₄ in the general formula (IV), and preferred ranges are also the same.

In the formula, L ₁ , L ₂ , L ₃ , n ₁ , Rp ₁ , Rp ₂ , Rp ₃ , Rp ₄ , Rp ₅ , Rp ₆ , Rp ₂₁ , Rp ₂₂ are synonymous with the general formula (pI), The preferable range is also the same. Rp ₅₁ , Rp ₅₂ , Rp ₅₃ , Rp ₅₄ , Rp ₅₅ , Rp ₅₆ are synonymous with R ₄₁ , R ₄₄ , R ₄₅ , R ₄₆ , R ₄₇ , R ₄₈ in the general formula (V), and preferred ranges are also the same. It is.
The compound represented by the general formula (pI) is preferably a compound represented by the following general formula (pIV).

In the formula, Z ₁ , L ₁ , L ₂ , L ₃ , n ₁ , Rp ₁ , Rp ₂ , Rp ₃ , Rp ₄ , Rp ₅ , Rp ₆ are synonymous with the general formula (pI), and preferred ranges are also included. It is the same.
Rp ₇ to Rp ₁₁ and Rp ₁₂ to Rp ₁₆ each independently represents a hydrogen atom or a substituent. However, the case where all of Rp ₇ to Rp ₁₁ and Rp ₁₂ to Rp ₁₆ are hydrogen atoms is excluded. Further, adjacent ones of Rp ₇ to Rp ₁₁ and Rp ₁₂ to Rp ₁₆ may be bonded to each other to form a ring. Further, Rp ₃ and Rp ₇ , Rp ₆ and Rp ₁₆ may be connected to each other.

In the general formula (pIV), Rp ₇ to Rp ₁₁ and Rp ₁₂ to Rp ₁₆ each independently represents a hydrogen atom or a substituent. However, all of Rp ₇ to Rp ₁₁ and Rp ₁₂ to Rp ₁₆ do not become hydrogen atoms. When Rp ₃ and Rp ₇ or Rp ₆ and Rp ₁₆ are linked, all other Rp ₈ to Rp ₁₁ and Rp ₁₂ to Rp ₁₅ may be hydrogen atoms.
If _{_{_{Rp 7 ~ Rp 11, Rp 12}}} ~ Rp 16 represents a _substituent, but the substituent represented by _{_{Rp 7 ~ Rp 11, Rp 12}} ~ Rp 16 include the substituent W described below, in particular a halogen atom, an alkyl Group, aryl group, heterocyclic group, hydroxy group, nitro group, alkoxy group, aryloxy group, heterocyclic oxy group, amino group, alkylthio group, arylthio group, alkenyl group, cyano group and heterocyclic thio group are preferred.
Rp ₇ to Rp ₁₁ and Rp ₁₂ to Rp ₁₆ are each independently a hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, hydroxy group, nitro group, alkoxy group, aryloxy group, heterocyclic oxy group, It is preferably an amino group, an alkylthio group, an arylthio group, an alkenyl group, a cyano group or a heterocyclic thio group, more preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group or a heterocyclic group. A hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, A heterocyclic group consisting of a 5-membered, 6-membered or 7-membered ring or a condensed ring thereof is more preferable. Group, an alkenyl group having 2 to 12 carbon atoms, an alkyloxy group having 1 to 12 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a 5-membered or 6-membered ring or a condensed ring thereof A heterocyclic group consisting of
In the case of an alkyl group, it may be linear or branched. Examples of the hetero atom contained in the heterocyclic group include an oxygen atom, a sulfur atom, and a nitrogen atom.
Specific examples of the alkyl group, alkenyl group, aryl group and the like include groups exemplified by the alkyl group, alkenyl group, and aryl group of the substituent W described later.

Further, adjacent ones of Rp ₇ to Rp ₁₁ and Rp ₁₂ to Rp ₁₆ may be bonded to each other to form a ring. Examples of the ring formed include ring R described later. The ring to be formed is preferably a benzene ring, a naphthalene ring, an anthracene ring, a pyridine ring, a pyrimidine ring or the like.
Further, Rp ₃ and Rp ₇ , Rp ₆ and Rp ₁₆ may be connected to each other. When Rp ₃ and Rp ₇ or Rp ₆ and Rp ₁₆ are linked, it becomes a condensed ring of 4 or more rings containing a naphthylene group and a phenyl group. The linkage between Rp ₃ and Rp ₇ or Rp ₆ and Rp ₁₆ may be a single bond.

The compound represented by the general formula (II) is a compound described in JP-A-2000-297068, and a compound not described in the above publication can also be produced according to the synthesis method described in the above publication. . Specific examples of the compound represented by the general formula (II) are shown below, but the present invention is not limited thereto. For example, among the specific examples of the general formula (II), the following compound 3 is used as a photoelectric conversion material, and the compound 3 is a powder.

An n-type organic semiconductor (compound) is an acceptor organic semiconductor (compound), which is represented by mainly an electron-transporting organic compound and refers to an organic compound having a property of easily accepting electrons. More specifically, the organic compound having the higher electron affinity when two organic compounds are used in contact with each other. Therefore, as the acceptor organic compound, any organic compound can be used as long as it is an electron-accepting organic compound. For example, condensed aromatic carbocyclic compounds (naphthalene, anthracene, fullerene, phenanthrene, tetracene, pyrene, perylene, fluoranthene, or derivatives thereof), 5- to 7-membered heterocyclic compounds containing nitrogen atom, oxygen atom, sulfur atom (E.g. pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxaline, quinazoline, phthalazine, cinnoline, isoquinoline, pteridine, acridine, phenazine, phenanthroline, tetrazole, pyrazole, imidazole, thiazole, oxazole, indazole, benzimidazole, benzotriazole, Benzoxazole, benzothiazole, carbazole, purine, triazolopyridazine, triazolopyrimidine, tetrazaindene, oxadia Metal, imidazopyridine, pyralidine, pyrrolopyridine, thiadiazolopyridine, dibenzazepine, tribenzazepine, etc.), polyarylene compounds, fluorene compounds, cyclopentadiene compounds, silyl compounds, nitrogen-containing heterocyclic compounds as ligands A complex etc. are mentioned.
Note that the present invention is not limited thereto, and as described above, any organic compound having an electron affinity higher than that of the organic compound used as the donor organic compound may be used as the acceptor organic semiconductor.

As the n-type organic semiconductor, fullerene or fullerene derivatives are preferably used. Fullerene C ₆₀ , fullerene C ₇₀ , fullerene C ₇₆ , fullerene C ₇₈ , fullerene C ₈₀ , fullerene C ₈₂ , fullerene C ₈₄ , fullerene C ₉₀ , fullerene C ₉₆ , fullerene C ₂₄₀ , fullerene C ₅₄₀ , mixed Fullerene and fullerene nanotube are represented, and a fullerene derivative represents a compound having a substituent added thereto. As the substituent, an alkyl group, an aryl group, or a heterocyclic group is preferable.

In the photoelectric conversion layer 152, the compound (organic material) represented by the general formula (II) exemplified as a preferred example of the p-type organic semiconductor is used as the photoelectric conversion material.
The thickness of the photoelectric conversion layer 152 is preferably 10 nm to 1000 nm, more preferably 50 nm to 800 nm, and particularly preferably 100 nm to 500 nm. By setting the thickness of the photoelectric conversion layer 152 to 10 nm or more, a suitable dark current suppressing effect can be obtained, and by setting the thickness of the photoelectric conversion layer 152 to 1000 nm or less, preferable photoelectric conversion efficiency can be obtained.

Note that the photoelectric conversion element 110 shown in FIG. 3, the substrate 112, and the insulating layer 114 constitute an imaging element. The image pickup device is used by being mounted on an image pickup device such as a digital camera or a digital video camera, an image pickup module such as an electronic endoscope or a mobile phone.

Next, the vapor deposition method of the vapor deposition apparatus 10 will be described more specifically by taking the method of forming the electron blocking layer 150 and the photoelectric conversion layer 152 of the photoelectric conversion element 110 shown in FIG. 3 as an example.
First, as shown in FIG. 4A, a first connection portion 144, a second connection portion 146, and a wiring layer 148 are formed on a substrate 112 on which a readout circuit 140 and a counter electrode voltage supply portion 142 are formed. A circuit substrate 111 (CMOS substrate) on which an insulating layer 114 provided with is formed is prepared. Then, the pixel electrode 116 is formed on the surface 114 a of the insulating layer 114 so as to be connected to each first connection portion 144.
In this case, as described above, the first connection portion 144 and the readout circuit 140 are connected, and the second connection portion 146 and the counter electrode voltage supply portion 142 are connected.

Next, as shown in FIG. 4B, an electron blocking material (organic material) is deposited using the vapor deposition apparatus 10 so as to cover all the pixel electrodes 116 except on the second connection portion 146. The electron blocking layer 150 is formed. As the electron blocking material, for example, the powdery compound 1 is used.

Next, using the vapor deposition apparatus 10, as shown in FIG. 4C, a photoelectric conversion material (organic material) is vapor-deposited on the surface 150 a of the electron blocking layer 150 to form the photoelectric conversion layer 152. For the photoelectric conversion material, for example, the powdery compound 3 is used. Thereby, the photoelectric conversion layer 152 is formed, and the organic layer 118 is formed.

Next, the counter electrode 120 is formed under a predetermined vacuum using, for example, a sputtering method in a pattern that covers the organic layer 118 and is formed on the second connection portion 146.
Next, a protective film 122 is formed on the surface 114 a of the insulating layer 114 so as to cover the counter electrode 120.

Next, the color filter 126, the partition wall 128, and the light shielding layer 129 are formed on the surface 122a of the protective film 122 by using, for example, a photolithography method. The formation process of the color filter 126, the partition wall 128, and the light shielding layer 129 may be under a predetermined vacuum or non-vacuum.
Next, the overcoat layer 130 is formed using, for example, a coating method so as to cover the color filter 126, the partition wall 128, and the light shielding layer 129. Thereby, the photoelectric conversion element 110 shown in FIG. 3 can be formed.

When manufacturing the photoelectric conversion element 110, the organic material used for film-forming of the electron blocking layer 150 and the photoelectric converting layer 152 is decomposed | disassembled by forming the electron blocking layer 150 and the photoelectric converting layer 152 using the vapor deposition apparatus 10. In addition, it is possible to deposit with a stable composition without deteriorating the purity of the organic material. For this reason, the electron blocking layer 150 and the photoelectric conversion layer 152 can be formed of high-purity films.

Next, a second embodiment of the present invention will be described.
FIG. 5 is a schematic view showing a main part of an organic material vapor deposition apparatus according to the second embodiment of the present invention. In FIG. 5, illustration of components other than the material supply unit 20 and the evaporation chamber 70 of the vapor deposition apparatus 10 a of the second embodiment is omitted.
In the present embodiment, the same components as those of the vapor deposition apparatus 10 of the first embodiment are denoted by the same reference numerals, and detailed description thereof is omitted.

Since the vapor deposition apparatus 10a of this embodiment is the structure similar to the vapor deposition apparatus 10 of 1st Embodiment except the structure of the evaporation chamber 70 differing from the vapor deposition apparatus 10 of 1st Embodiment, Detailed description thereof is omitted.
In the evaporation chamber 70, the housing 72 and the material filling portion 74 have an integral structure, and the bottom of the housing 72 is the material filling portion 74. The housing 72 has a substantially conical shape with the material filling portion 74 as a bottom surface, and becomes narrower toward the top of the housing 72. Moreover, the upper end of the housing 72 is opened, and the material supply path 24 of the material supply unit 20 is connected to the opening. By narrowing the upper portion of the housing 72, the amount of the vapor Vo adhering to the upper portion of the housing 72 can be reduced.

The

induction heating coils

48a and 48b are composed of a single coil and are connected to a high-frequency power source 50 (see FIG. 1), although not shown. The induction heating coil 48 a provided on the upper portion of the housing 72 is arranged at a narrower pitch than the induction heating coil 48 b provided in the material filling unit 74.
In the present embodiment, since the pitch of the induction heating coil 48 a on the upper portion of the housing 72 is narrowed, the temperature at the upper portion of the housing 72 is higher than that of the material filling portion 74 without particularly controlling as described above. Can be.
The heat radiation member 47 is directly connected to the bottom surface 74 a and the side surface 74 b of the material filling portion 74 of the housing 72. The heat radiating member 47 has, for example, a fin shape. In addition, the heat radiating member 47 is not limited to a fin-shaped thing, The various hollow member of the vapor deposition apparatus 10 of the above-mentioned 1st Embodiment can also be used.

Also in the vapor deposition apparatus 10a of this embodiment, the effect similar to the vapor deposition apparatus 10 of 1st Embodiment is acquired. As described above, due to the pitch of the induction heating coils 48 a and 49 b and the heat radiating member 47, in the evaporation chamber 70, the temperature of the material filling portion 74 (the bottom portion of the casing 72) is always lower than the upper portion of the casing 72. it can. For this reason, temperature can be made high in order of the material filling part 74 (bottom part of the housing 72), the upper part of the housing 72, and the vapor | steam guide part 60 (transport pipe 62 and the discharge part 64). Thereby, as described above, the generation of cold spots can be suppressed during vapor deposition, and the organic material m can be vapor-deposited with a stable composition without causing deterioration in purity and decomposition of the organic material.
In the vapor deposition apparatus of any of the above-described embodiments, the organic material used for vapor deposition is not limited to the organic material used for the production of organic CMOS, but is an NPD (naphthyl-substituted diamine derivative) used for the production of organic EL. ) And Alq (a complex of hydroxyquinoline and aluminum) can also be used. Even in this case, it goes without saying that the above-described effects can be obtained.

The present invention is basically configured as described above. As mentioned above, although the vapor deposition apparatus of the organic material of this invention was demonstrated in detail, this invention is not limited to the said embodiment, In the range which does not deviate from the main point of this invention, it is possible to perform various improvement or a change. Of course.

DESCRIPTION OF SYMBOLS 10 Deposition apparatus 12 Vacuum container 14 Vacuum exhaust part 16 Control part 20 Material supply part 22 Material stock room 24 Material supply path 26 Supply valve 28 Heat insulation pipe 30

Heating valve

40, 70

Evaporation chamber

42, 72

Housing

44, 74 Material filling part DESCRIPTION OF SYMBOLS 50 High frequency power supply 60 Steam guide part 62 Transport pipe 64 Discharge part 66 Heater 68

Power supply part

100, 112 Substrate 110 Photoelectric conversion element 114 Insulating layer 116 Pixel electrode 118 Organic layer 120 Counter electrode 122 Protective film 126 Color filter 130 Overcoat layer 150 Electron Blocking layer 152 Photoelectric conversion layer

Claims

A vapor deposition apparatus that deposits an organic material on a material to be deposited in a vacuum atmosphere,
An evaporation chamber in which the organic material is disposed and the organic material is heated to evaporate;
A guide portion for guiding the vapor of the organic material generated in the evaporation chamber to the film forming material,
The vapor deposition apparatus for organic materials, wherein the evaporation chamber is always kept at a temperature lower than that of the guide portion.
2. The organic material deposition apparatus according to claim 1, wherein the heating method of the evaporation chamber is an induction heating method.
The evaporation chamber has a filling portion in which the organic material is disposed at the bottom,
The organic material vapor deposition apparatus according to claim 1, wherein a heat radiating member is provided at least at a bottom portion of a bottom portion and a side surface of the filling portion.
4. The organic material vapor deposition apparatus according to claim 3, wherein the heat radiating member is a hollow cylindrical member and is directly connected to the filling portion.
5. The organic material vapor deposition apparatus according to claim 4, wherein the heat radiating member is connected to the filling portion by welding.
The control unit according to any one of claims 3 to 5, further comprising a control unit that separately controls the temperature in the first region where the filling unit is located and in the second region other than the filling unit. Organic material vapor deposition equipment.
6. The induction heating coil is arranged in the evaporation chamber with a pitch of the second region other than the filling portion being narrower than a pitch of the first region having the filling portion. The organic material vapor deposition apparatus according to Item.