JP2012243873A - Membrane, method for producing the same, and photoelectric conversion element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for performing continuous vapor deposition of an organic material, which is not suitable for sublimation purification, for a prolonged period of time in a stable manner without decreasing its purity.SOLUTION: A membrane is obtained by subjecting an organic material that cannot be purified by sublimation purification to vapor deposition including: using a material for vapor deposition containing the organic material and a compound (A) having a boiling point or sublimation point Tlower than a vapor deposition temperature Tof the organic material; heating the material for vapor deposition by first heating to a temperature Thigher than the boiling point or sublimation point Tof the compound (A) and lower than the vapor deposition temperature Tof the organic material to keep the material at the temperature T; and after the first heating 1, heating the material for vapor deposition by second heating to a temperature equal to or higher than the evaporation temperature Tof the organic material and equal to or lower than a decomposition temperature of the organic material to keep the material at the temperature.

Description

  The present invention relates to a film, a film manufacturing method, and a photoelectric conversion element. More specifically, when vapor deposition film formation is performed using an organic material that is not suitable for sublimation purification, a method for producing a high-purity film, a film obtained by the production method (particularly preferably a photoelectric conversion film), The present invention relates to a photoelectric conversion element having a conversion film.

  Organic photoelectric conversion films made of organic materials are used in photoelectric conversion elements, imaging elements, optical sensors, solar cells, and the like, and studies have been made on improving photoelectric conversion efficiency and reducing dark current. For example, Patent Document 1 describes an element in which a bulk hetero film made of an organic material having a specific structure and fullerenes is used as an organic photoelectric conversion film.

Usually, organic materials contain impurities such as unreacted substances, intermediate products, and solvents derived from the synthesis process, etc., and as they are as organic electronics materials such as materials for photoelectric conversion elements and materials for organic electroluminescence elements. When used, it is known that the impurities adversely affect device performance.
Therefore, purification methods such as column chromatography, recrystallization, reprecipitation purification, and sublimation purification have been used as methods for removing impurities contained in organic materials. In particular, sublimation purification is performed without a solvent, so that contamination of impurities contained in the solvent and residual solvent in the material (which causes a decrease in the degree of vacuum during vacuum deposition performed in device fabrication) can be suppressed. It is widely used as a purification method for obtaining pure organic electronics materials.
Then, when an organic film such as a photoelectric conversion film is formed using the purified organic material, for example, a uniform film formation is easy, and the possibility of contamination by impurities can be reduced as compared with a coating method. The film formation by is preferably used.

However, even organic materials that exhibit excellent performance (for example, photoelectric characteristics such as sensitivity, dark current, and responsiveness) are vulnerable to heat, and there are organic materials to which sublimation purification treatment cannot be applied. Conventionally, when such an organic material is vapor-deposited as it is, the vapor deposition temperature is controlled by raising the temperature at a certain gradient so that the material does not bump or overshoot the vaporization temperature of the material, and at a desired vaporization temperature. The film was deposited after waiting for the degree of vacuum and the deposition rate to stabilize. When vapor deposition is performed by such a method, the purity of the obtained film is remarkably lowered (the element performance is also lowered), or the degree of vacuum in the film formation chamber is deteriorated after a while from the start of vapor deposition.
That is, an organic material that is weak against heat and cannot be subjected to sublimation purification treatment cannot be continuously vapor-deposited for a long time, is inferior in productivity, and lowers the purity and performance of the obtained film.

Here, the difference between sublimation purification and vapor deposition will be described. Generally, in sublimation purification, in order to take out a high-purity material, it is necessary to create an atmospheric flow (gas flow) in a sublimation tube, and the degree of vacuum is as low as about 10 ⁻² Pa. On the other hand, vapor deposition does not require the atmosphere in the chamber and is in a vacuum state, so a high vacuum of about 10 ⁻⁵ Pa is obtained. When a material having the same sublimation point is heated and volatilized, it is necessary to heat at a higher temperature when the degree of vacuum is lower (higher pressure). Therefore, according to the above degree of vacuum, (sublimation purification temperature) > (Deposition temperature).
Moreover, when the decomposition temperature of the organic compound to be volatilized is higher than the sublimation purification temperature, it is difficult to cause a problem. However, when the relationship of (sublimation purification temperature)> (material decomposition temperature)> (deposition temperature) is satisfied, vapor deposition can be performed. However, sublimation purification is not possible.

  For example, Patent Documents 2 to 5 describe the sublimation purification and vapor deposition of a material containing a compound having a lower boiling point or sublimation point than the target compound, but none of the above problems has been studied.

JP 2010-103457 A JP 2008-294003 A JP 2006-161074 A JP 2006-283086 A JP 2002-114743 A

In view of the above circumstances, an object of the present invention is to provide a film containing an organic material not suitable for sublimation purification with high purity, a method for producing the film, and a photoelectric conversion element including the film.
It is another object of the present invention to provide a method for continuously depositing an organic material that is not suitable for sublimation purification stably for a long time without lowering the purity.

As a result of intensive studies, the inventors of the present invention use a vapor deposition material containing an organic material not suitable for sublimation purification and a compound (A) having a boiling point or sublimation point lower than that of the organic material, and performing two-step heating at a specific temperature. Thus, the present inventors have found that the organic material can be deposited in a highly purified state, and stable deposition can be performed for a long time without causing material decomposition.
That is, the specific means for achieving the above-described problem is as follows.

[1]
A film obtained by vapor deposition of an organic material that cannot be purified by sublimation purification,
Using a vapor deposition material containing the organic material and a compound (A) having a boiling point or sublimation point T ₁ lower than the vapor deposition temperature T ₃ of the organic material,
The deposition material is heated to a temperature T _{2 that} is higher than the boiling point or sublimation point T ₁ of the compound (A) and lower than the deposition temperature T _{3 of the} organic material by the first heating, and then reaches the temperature T ₂ . Maintain,
After the first heating, the second heating, the deposition temperature T ₃ or more organic materials, after raising the temperature to the decomposition temperature below the temperature of the organic material, a vapor deposited film formation of the organic material was maintained at this temperature A membrane obtained by performing.
Here, the boiling point or sublimation point T ₁ of the compound (A) is the boiling point or sublimation point of the compound (A) at 1.0 × 10 ⁻¹ Pa.
Deposition temperature T ₃ of the organic material refers to the temperature at which the deposition rate of the organic material reaches the 0.5 Å / sec.
The decomposition temperature of an organic material refers to a temperature at which weight loss of 1% or more occurs when the organic material is heated at a constant temperature for 60 minutes in differential thermogravimetry.
[2]
The film according to [1], wherein the second heating is started after the compound (A) has evaporated or sublimated.
[3]
The film according to [2], wherein the second heating is started after confirming that the compound (A) has evaporated or sublimated by the value of the degree of vacuum in the film forming chamber.
[4]
The film according to any one of [1] to [3], wherein the organic material is an organic material used for forming a photoelectric conversion film.
[5]
The film according to any one of [1] to [4], wherein the organic material is a donor-acceptor type dye compound represented by the following general formula (I).
Formula (I)

(D represents an atomic group having a hetero atom. A represents a group having a carbonyl group or a cyano group. L ₂ and L ₃ each independently represent an unsubstituted methine group or a substituted methine group. N represents 0. (It represents the integer above.)
[6]
The film according to any one of [1] to [5], wherein the organic material is a compound represented by the following general formula (II).
Formula (II)

(In the formula, 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, D ₁ represents an atomic group having a hetero atom, and n represents an integer of 0 or more.)
[7]
The film according to any one of [1] to [6], wherein the compound (A) is an organic solvent having a boiling point of 120 ° C. or higher at 1.0 × 10 ⁻¹ Pa.
[8]
The film according to any one of [1] to [7], wherein the compound (A) is dimethylacetamide, 1-ethyl-2-pyrrolidone, or N, N-dimethylformamide.
[9]
The difference between the boiling point or sublimation point _{T 1} of the deposition temperature _{T 3} and the compound of the organic material (A) is a 50 to 160 ° C., [1] film according to any one of - [8].
[10]
The difference between the _{T 1} and _{T 2} is a 30 to 100 ° C., [1] ~ film of any one of [9].
[11]
The difference between the _{T 2} and _{T 3} are the 10 to 60 ° C., [1] ~ film of any one of [10].
[12]
A photoelectric conversion element having a transparent conductive film, a photoelectric conversion film, and a conductive film in this order, wherein the photoelectric conversion film is a film according to any one of [1] to [11]. Photoelectric conversion element.
[13]
A method for producing a film obtained by vapor deposition of an organic material that cannot be purified by sublimation purification,
Using a vapor deposition material containing the organic material and a compound (A) having a boiling point or sublimation point T ₁ lower than the vapor deposition temperature T ₃ of the organic material,
The deposition material is heated to a temperature T _{2 that} is higher than the boiling point or sublimation point T ₁ of the compound (A) and lower than the deposition temperature T _{3 of the} organic material by the first heating, and then reaches the temperature T ₂ . Maintain,
After the first heating, the second heating, the deposition temperature T ₃ or more organic materials, after raising the temperature to the decomposition temperature below the temperature of the organic material, a vapor deposited film formation of the organic material was maintained at this temperature A method for producing a film.
Here, the boiling point or sublimation point T ₁ of the compound (A) is the boiling point or sublimation point of the compound (A) at 1.0 × 10 ⁻¹ Pa.
Deposition temperature T ₃ of the organic material refers to the temperature at which the deposition rate of the organic material reaches the 0.5 Å / sec.
The decomposition temperature of an organic material refers to a temperature at which weight loss of 1% or more occurs when the organic material is heated at a constant temperature for 60 minutes in differential thermogravimetry.

ADVANTAGE OF THE INVENTION According to this invention, the film | membrane and the manufacturing method of this film | membrane which contain the organic material which is not suitable for sublimation purification with high purity can be provided.
In addition, according to the present invention, it is possible to provide a method of continuously depositing an organic material that is not suitable for sublimation purification stably for a long time without lowering the purity.

FIG. 1A and FIG. 1B are schematic cross-sectional views each showing a configuration example of the photoelectric conversion element according to the present invention. It is a cross-sectional schematic diagram for one pixel of the image sensor according to the present invention. It is a conceptual diagram for demonstrating the manufacturing method of the film | membrane of this invention. 3 is a schematic diagram showing the relationship between temperature and pressure in the vapor deposition process of Example 1. FIG. It is the schematic diagram which showed the relationship between the temperature and pressure in the vapor deposition process of the comparative example 1 (conventional method).

  Hereinafter, the present invention will be described in detail. In the present specification, “to” indicates a range including the numerical values described before and after the minimum and maximum values, respectively.

[Film Production Method (Organic Material Deposition Method)]
The present invention is a film obtained by vapor deposition of an organic material that cannot be purified by sublimation purification,
Using a vapor deposition material containing the organic material and a compound (A) having a boiling point or sublimation point T ₁ lower than the vapor deposition temperature T ₃ of the organic material,
The deposition material is heated to a temperature T _{2 that} is higher than the boiling point or sublimation point T ₁ of the compound (A) and lower than the deposition temperature T _{3 of the} organic material by the first heating, and then reaches the temperature T ₂ . Maintain,
After the first heating, the second heating, the deposition temperature T ₃ or more organic materials, after raising the temperature to the decomposition temperature below the temperature of the organic material, a vapor deposited film formation of the organic material was maintained at this temperature It is related with the film | membrane obtained by performing.
Further, the present invention is a method for producing a film obtained by vapor deposition of an organic material that cannot be purified by sublimation purification,
Using a vapor deposition material containing the organic material and a compound (A) having a boiling point or sublimation point T ₁ lower than the vapor deposition temperature T ₃ of the organic material,
The deposition material is heated to a temperature T _{2 that} is higher than the boiling point or sublimation point T ₁ of the compound (A) and lower than the deposition temperature T _{3 of the} organic material by the first heating, and then reaches the temperature T ₂ . Maintain,
After the first heating, the second heating, the deposition temperature T ₃ or more organic materials, after raising the temperature to the decomposition temperature below the temperature of the organic material, a vapor deposited film formation of the organic material was maintained at this temperature It also relates to a method of manufacturing a membrane.
Here, the boiling point or sublimation point T ₁ of the compound (A) is the boiling point or sublimation point of the compound (A) at 1.0 × 10 ⁻¹ Pa.
Deposition temperature T ₃ of the organic material refers to the temperature at which the deposition rate of the organic material reaches the 0.5 Å / sec.
The decomposition temperature of an organic material refers to a temperature at which weight loss of 1% or more occurs when the organic material is heated at a constant temperature for 60 minutes in differential thermogravimetry.
Hereinafter, a method for producing a film according to the present invention (an organic material vapor deposition method according to the present invention) will be described.

  As described above, it is considered that the factor that deteriorates the vapor deposition performance of the organic material that is not suitable for sublimation purification is the decomposition of the material by heat. As a mechanism of this material decomposition, when a certain amount of impurities remain in the organic material and vapor deposition is performed by raising the temperature to the evaporation temperature of the organic material, the organic material is It is estimated that the melting point is lowered and decomposition by heat is promoted. In addition, after vapor deposition with a certain amount of impurities remaining in the organic material as described above, the purity of the residual organic material remaining in the crucible was examined. Was found to be low. Furthermore, it was found from the HPLC spectrum that the cause of the deterioration of the degree of vacuum when deposited in this way is due to the decomposition of the organic material.

According to the study by the present inventors, a compound (A) having a boiling point or sublimation point T ₁ lower than the vapor deposition temperature T _{3 of the} organic material is added to a vapor deposition material containing an organic material that cannot be purified by sublimation purification, After confirming that the compound (A) has completely evaporated or sublimated, it is possible to carry out vapor deposition film formation in a high purity state by starting the vapor deposition film formation of the organic material, without causing material decomposition. Long-term stable deposition became possible. It has a boiling point or sublimation point of the impurity contained in the organic material, because the it is lower than the deposition temperature T ₃ of the organic material, at the time when the compound (A) is fully evaporated or sublimed, and the impurity Most of them are evaporated or sublimated, and at the time of starting the deposition of the target organic material, the deposited material contains almost no impurities, and the film formation process of the organic material can be performed with high purity. It is presumed that the lowering of the melting point of the organic material due to this and the decomposition by heat hardly occur.
Moreover, since the photoelectric conversion film obtained by the vapor deposition method of the present invention has high purity, it is possible to obtain a photoelectric conversion element with higher performance than before.

In the present invention, the first heating is performed to raise the temperature to a temperature T ₂ higher than the boiling point or sublimation point T ₁ of the compound (A) and lower than the vapor deposition temperature T _{3 of the} organic material, and then maintain the temperature T _2. after the first heating, the organic material deposition temperature T ₃ or more, the temperature was raised up to the decomposition temperature below the temperature of the organic material is performed and a second heating to maintain the temperature, the in the second heating It is preferable to deposit an organic material. Thereby, the impurities and the compound (A) originally contained in the organic material are removed in the first heating, and vapor deposition can be performed with a high-purity organic material in the second heating.

  From the viewpoint of lowering the concentration of impurities in the vapor deposition material, it is preferable to end the first heating and start the second heating after the compound (A) has evaporated or sublimated. More preferably, after all the compound (A) has evaporated or sublimated, the first heating is terminated and the second heating is started.

  Furthermore, it is preferable to confirm that the compound (A) has evaporated or sublimated by the value of the degree of vacuum in the film forming chamber. By using the degree of vacuum as an index, it is easy to see whether the compound (A) has completely evaporated or sublimated, and the vapor deposition method according to the present invention can be easily performed. When the compound (A) begins to evaporate or sublimate, the degree of vacuum proceeds in a worsening direction, and when the compound (A) evaporates or sublimates to some extent, the degree of vacuum improves. When the degree of vacuum is the same as the initial level or when it is slightly improved, it can be determined that all of the compound (A) has evaporated or sublimated.

  Next, although an example of the preferable embodiment of the vapor deposition method concerning this invention is demonstrated more concretely using figures, this invention is limited to the following specific examples, and should not be interpreted.

FIG. 3 is a diagram showing an example of a temperature profile (upper figure) and a vacuum degree profile (lower figure) during vapor deposition of the vapor deposition method according to the present invention and the conventional vapor deposition method.
In the temperature profile (upper figure) and the vacuum degree profile (lower figure), the time on the horizontal axis corresponds.

In the conventional vapor deposition method shown by the solid line in FIG. 3, the vapor deposition material contains only the organic material, and the temperature is raised to the vapor deposition temperature T ₃ of the organic material at once. The degree of vacuum worsens with time. This is thought to be due to the lowering of the melting point of the organic material due to impurities and the decomposition of the organic material.

In contrast, in the vapor deposition method according to the present invention indicated by the broken line in FIG. 3, the organic material and the compound (A) having a boiling point or sublimation point T ₁ lower than the vapor deposition temperature T ₃ of the organic material are contained. The evaporation material is used. And the following behavior is shown.
1. The temperature is raised to a temperature T ₂ between the boiling point or sublimation point T ₁ of the compound (A) and the vapor deposition temperature T ₃ of the organic material, and kept at a constant temperature.
2. From around reached the boiling point or sublimation point T ₁ of the compound (A), results in a change in the direction in which the vacuum degree is deteriorated.
3. When continues to heat at a temperature T _2, it begins to change in a direction in which the degree of vacuum is improved again.
4). Degree of vacuum upon reaching better than comparable or initial state heated before initial state (P0), is heated to the deposition temperature T ₃ of the organic material.
5. Therefore, a minute change in the degree of vacuum occurs again. It is believed that the impurities having a boiling point or sublimation point in the range of T ₂ through T ₃ are evaporated or sublimated.
6). After confirming that the change in the degree of vacuum is equal to or better than the degree of vacuum before the temperature rise of T ₂ → T ₃ and that the deposition rate of the organic material is stabilized, the film forming process is started.

The difference between the vapor deposition temperature T _{3 of the} organic material and the boiling point or sublimation point T ₁ of the compound (A) may be more than a certain difference because the organic material and the compound (A) are separated and fly away. It is preferable that the temperature is from 50 to 160 ° C. from the viewpoint of being preferable and, if the difference is too large, the phenomenon of low melting point may occur due to unevenness in the distribution of impurities in the temperature difference range. 70 to 120 ° C. is more preferable.
From the viewpoint that the melting point of the organic material due to impurities is not lowered, and is sufficiently higher than the boiling point of the compound (A), the difference between T ₁ and T ₂ is preferably 30 to 100 ° C. More preferably, it is 50-80 degreeC.
T ₂ and T ₃ are preferably close to each other because there are impurities trapped in the molecule of the organic material that cannot be sufficiently skipped at T _2. However, if they are too close, they can only fly at a temperature higher than T _2. It is preferable to have a certain temperature interval, and the difference between T ₂ and T ₃ is preferably 10 to 60 ° C. More preferably, it is 40 degreeC.
As described later, the boiling point or sublimation point _{T 1} is preferably 120 to 200 [° C. of the compound (A), more preferably from 160 to 180 ° C..

In the vapor deposition method according to the present invention, the initial degree of vacuum is not particularly ^limited, 10 -5 ^{Pa to 10} -4 Pa is ^{preferably, 4.0 × 10 -5 Pa~1.2 × 10} -4 Pa Gayori preferable.
The rate of temperature increase is not particularly limited, but is preferably 5 to 30 ° C / min, and more preferably 10 to 25 ° C / min.

[Organic materials]
The organic material according to the present invention will be described.
The organic material according to the present invention cannot be purified by sublimation purification.
The organic material according to the present invention is preferably a material (photoelectric conversion material) used for forming a photoelectric conversion film.
The vapor deposition temperature of the organic material is preferably 200 to 290 ° C. under a pressure of 7 × 10 ⁻⁵ Pa, and is preferably equal to or lower than the decomposition temperature of the organic material.
Here, the vapor deposition temperature of the organic material refers to a temperature at which the vapor deposition rate of the organic material reaches 0.5 Å / second. The pressure in the film forming chamber when measuring the vapor deposition temperature of the organic material is preferably 1.0 × 10 ⁻⁴ Pa or less.

The decomposition temperature of the organic material is preferably about 210 to 300 ° C.
Here, the decomposition temperature of the organic material refers to a temperature at which weight loss of 1% or more occurs when the organic material is heated at a constant temperature for 60 minutes in differential thermogravimetry. In differential thermogravimetric measurement, it is preferable to measure at a pressure of 1.0 × 10 ⁻¹ Pa or less.

The organic material is preferably a donor-acceptor type dye compound represented by the following general formula (I).
Formula (I)

(D represents an atomic group having a hetero atom. A represents a group having a carbonyl group or a cyano group. L ₂ and L ₃ each independently represent an unsubstituted methine group or a substituted methine group. N represents 0. (It represents the integer above.)

  The donor-acceptor type dye compound represented by the general formula (I) is a compound that is easily decomposed when the donor part D melts, and thus has a melting point and a material decomposition temperature close to each other. A compound.

  Said D represents the atomic group which has a hetero atom. Examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom.

The organic material in the present invention is preferably a compound represented by the following general formula (II). The compound represented by the general formula (II) is also used as a p-type organic semiconductor in the photoelectric conversion element.
Formula (II)

(In the formula, 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, D ₁ represents an atomic group having a hetero atom, and n 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 a 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: Is 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- Zeon 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 and the like.
(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 its derivatives. 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, 1,3-diphenyl, 1,3-diaryl compounds such as 1,3-di (p-chlorophenyl) and 1,3-di (p-ethoxycarbonylphenyl), 1-alkyl-1-aryl compounds such as 1-ethyl-3-phenyl, Examples include 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-allylrhodanine, 3-arylrhodanine such as 3-phenylrhodanine, and 3- (2-pyridyl) rhodanine. And the like.

(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 and the like.
(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-imidazolidinedione 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 and the like.
(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 and the like.

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, a 2-thiobarbi acid nucleus, Tool 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 nucleus And more preferably a 1,3-dicarbonyl nucleus, a 2,4,6-triketohexahydropyrimidine nucleus (including a thioketone body, such as a barbituric acid nucleus, Bituric 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, such as barbituric acid nuclei, 2-thiobarbituric acid nuclei), particularly preferably 1,3-indandione nuclei, barbituric acid nuclei, 2-thiobarbituric acid nuclei and their derivatives. is there.

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

Z ³ represents a ring containing at least three carbon atoms and 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 above, preferably 1,3-dicarbonyl nucleus, 2,4,6-triketohexahydropyrimidine nucleus (including 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 the alkyl group, and 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).
Formula (IV)

R _{41 to} R ₄₄ each independently represents a hydrogen atom or a substituent.
General formula (V)

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, those exemplified as the substituent W can be applied. In addition, 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 , and R _{45 to} R ₄₈ each independently represent a hydrogen atom or a substituent. As the substituent, those exemplified 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 body), it is preferably a group represented by the following general formula (VI).
Formula (VI)

R ₈₁ and R ₈₂ each independently represents 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, those exemplified 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 (for example, 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 part is a nitrogen atom and those having a carbon atom are preferable. In the case of a nitrogen atom, an alkyl group (1 to 12 carbon atoms) or an aryl group (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, or 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. Substituted methine groups may combine 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 is preferably an aryl group substituted with —NR ^a (R ^b ) (preferably having 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, linked to L to 5 to 6 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 following general formula (VIII), (IX) or (X) 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, it is 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). The 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 the 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 ring. (Examples of the ring to be formed include a ring R described later, preferably a 6-membered ring).

General formula (IID)

In the formula, R _{1 to} R ₆ each independently represent 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.

Formula (III)

In the formula, 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 preferable that D ₁ is represented by the following general formula (VII).

Formula (VII)

In the formula, R _{91 to} R ₉₈ each independently represent 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. In addition, the bonding portion with L ₃ (L ₁ when n ₁ is 0) may be the position of R ₉₁ , R ₉₂ , R ₉₃ , and in that case, the bonding portion 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 part of the general formula (VII), R ₉₀ and R ₉₃ may be bonded to form a ring, and R ₉₂ is L ₃ (when n ₁ is 0). Is a bond to L ₁ ), and R ₉₀ is bonded to the bond of general formula (VII), R ₉₀ and R ₉₁ , and R ₉₀ and R ₉₃ are bonded to form a ring. In addition, when 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 preferably all 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, preferably an unsubstituted phenyl group.
m represents an integer of 0 or more, but 0 or 1 is preferable.

It is also preferred that D ₁ is a group represented by the general formula (VIII), (IX) or (X).

Formula (VIII)

_Wherein each is R 51 _{to R 54} independently represents 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.

Formula (IX)

In the formula, R _{61 to} R ₆₄ each independently represent 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.

Formula (X)

_Wherein, R 71 _{to R 73} each independently represent 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 (III) is more preferably used as the D ₁ .

In 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, R _{1 to} R ₄ are all 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. R ₅ and R ₆ 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 > -R < ₁₄ >, R < ₂₀ > -R < ₂₄ >, R < ₃₀ > -R < ₃₄ > represents a hydrogen atom or a substituent each independently. 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 ) are bonded to form two benzene rings adjacent to 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, but preferably an alkyl group (for example, a methyl group or an ethyl group) or an aryl group (for example, , Phenyl group, naphthyl group), and these groups may be further substituted with a substituent W (preferably an aryl group). Among _them, preferred is a case R _{20, R 30} is a substituent, and the other _{R 11 ~R 14, R 21 ~R} 24, R 31 ~R 34 is more preferably be a hydrogen atom.

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

  Formula (pI)

In the formula, 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 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 represent a hydrogen atom or a substituent. If Rp ₁ to Rp ₆ represents a _substituent, but examples of a substituent Rp 1 to Rp ₆ represents include the substituent W described below, in particular a 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, halogen atom, alkyl group, aryl group, heterocyclic group, hydroxy group, nitro group, alkoxy group, aryloxy group, heterocyclic oxy group, amino group, 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, or a carbon number. A 6-20 aryl group and a C4-C16 heterocyclic group are more preferable, a hydrogen atom, a C1-C12 alkyl group, and a C6-C14 aryl group are still more preferable, a hydrogen atom, carbon number 1 -6 alkyl groups and C6-C10 aryl groups are more preferred, and hydrogen atoms are particularly preferred. In the case of an alkyl group, there may be a branch. _Also, if Rp 1 to Rp ₆ is a substituent, it may have further substituents. Further substituents include the substituent W described below. When there are a plurality of the further substituents, the plurality of substituents may be connected 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 Rp _{21, Rp 22} represents preferably an aryl group having 6 to 30 carbon atoms, 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 (eg, methyl group, ethyl group, t-butyl group), an alkoxy group (eg, methoxy group, ethoxy group, isopropoxy group), and 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. The preferred substituents in the case of Rp _21, Rp ₂₂ has a substituent, 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, t- butyl Group, trifluoromethyl group, phenyl group, or 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).

  General formula (pII)

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 ₄₁ , Rp ₄₂ , Rp ₄₃ , Rp ₄₄ are synonymous with R ₄₁ , R ₄₂ , R ₄₃ , R ₄₄ in general formula (IV), and preferred ranges are also the same.

  General formula (pIII)

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).

  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 represent 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 General Formula (pIV), Rp _{7 to} Rp ₁₁ and Rp _{12 to} Rp ₁₆ each independently represent 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. In the case where Rp ₃ and Rp _7, or Rp ₆ and _{Rp 16} are linked, the other of _{Rp 8 ~Rp 11, Rp 12 ~Rp} 15 may be all a hydrogen atom.
When Rp _{7 to} Rp ₁₁ , Rp _{12 to} Rp ₁₆ represent a substituent, examples of the substituent represented by Rp _{7 to} Rp ₁₁ , Rp _{12 to} Rp ₁₆ include the substituent W described below. 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, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a hydroxy group, a nitro group, an alkoxy group, an aryloxy group, or a heterocyclic oxy group. , An amino group, an alkylthio group, an arylthio group, an alkenyl group, a cyano group or a heterocyclic thio group, and more preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, or a heterocyclic group. Preferably, 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 preferred, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms. 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. The heterocyclic group is more preferable.
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 connected, 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 general formula (I) or (II) can be manufactured according to the synthesis method of Unexamined-Japanese-Patent No. 2000-297068.
Specific examples of the compound represented by the general formula (I) or (II) are shown below, but the present invention is not limited thereto.

[Compound (A)]
In the present invention, said organic materials, compounds having a deposition temperature T low boiling point or sublimation point T ₁ than ₃ of the organic material (A) and the vapor deposition material containing used. In the present invention, the intention of adding the compound (A) to the vapor deposition material is that the change in the degree of vacuum is easier to understand than when the compound (A) is not added during the heating of the vapor deposition material, and is included in the organic material. This is because it is easy to determine whether or not the impurities that have been removed.
Here, the boiling point or sublimation point T ₁ of the compound (A) is the boiling point or sublimation point of the compound (A) at 1.0 × 10 ⁻¹ Pa.

Since the compound (A) can be an impurity or an impurity group, it is necessary to evaporate or sublime before the organic material is deposited.
As a compound (A), it is preferable that molecular weight is 50-200, and it is more preferable that it is 60-130.
The compound (A) is preferably an organic solvent in which the organic material is easily dissolved. When the organic material is easily dissolved, impurities such as a solvent trapped in the molecule of the organic material are easily evaporated together with the compound (A). The compound (A) is preferably an organic solvent having a boiling point of 120 ° C. or higher at 1.0 × 10 ⁻¹ Pa, more preferably an organic solvent having a boiling point of 120 to 200 ° C., and a boiling point of 160 to 180. More preferably, it is an organic solvent at 0 ° C.
As the compound (A), dimethylacetamide (DMAc, boiling point at 1.0 × 10 ⁻¹ Pa: 160 ° C.), 1-ethyl-2-pyrrolidone (NEP, boiling point at 1.0 × 10 ⁻¹ Pa: 180 ° C.) or N, N-dimethylformamide (DMF, boiling point at 1.0 × 10 ⁻¹ Pa: 130 ° C.) is particularly preferable.

  In the vapor deposition material in the present invention, the organic material and the compound (A) are preferably mixed so that the compound (A) is uniformly distributed in order to further reduce impurities. The compound (A) is preferably contained in an amount of 0.01 to 3.0% by mass, more preferably 0.1 to 2.0% by mass with respect to the organic material.

[Photoelectric conversion element]
The photoelectric conversion element according to the present invention includes a photoelectric conversion film formed by the vapor deposition method of the present invention. Since the photoelectric conversion film formed by the vapor deposition method of the present invention contains a high-purity organic material, a photoelectric conversion element with high sensitivity and low dark current can be obtained.
A preferred embodiment of the photoelectric conversion element has a transparent conductive film, a photoelectric conversion film, and a conductive film in this order, and the photoelectric conversion film preferably includes a photoelectric conversion layer and an electron blocking layer. Furthermore, a mode in which a conductive film, an electron blocking layer, a photoelectric conversion layer, and a transparent conductive film are stacked in this order is a more preferable mode.

In FIG. 1, the structural example of the photoelectric conversion element which concerns on embodiment of this invention is shown.
A photoelectric conversion element 10a shown in FIG. 1A includes a photoelectric conversion film (an electron blocking layer 16A and a photoelectric conversion layer 16A) formed on a lower electrode 11 on a conductive film 11 (hereinafter referred to as a lower electrode) that functions as a lower electrode. The photoelectric conversion layer 12) formed on the electron blocking layer 16A and the transparent conductive film (hereinafter referred to as the upper electrode) 15 functioning as the upper electrode are laminated in this order.
FIG. 1B shows a configuration example of another photoelectric conversion element. In the photoelectric conversion element 10b shown in FIG. 1B, a photoelectric conversion film (electron blocking layer 16A, photoelectric conversion layer 12, and hole blocking layer 16B) and an upper electrode 15 are laminated on the lower electrode 11 in this order. It is the structure which was made. Note that the stacking order of the electron blocking layer, the photoelectric conversion layer, and the hole blocking layer in FIGS. 1A and 1B may be reversed depending on the application and characteristics.
In such a configuration, it is preferable that light is incident on the photoelectric conversion film through the transparent conductive film.
Moreover, when using these photoelectric conversion elements, an electric field can be applied. In this case, the conductive film and the transparent conductive film serve as a pair of electrodes, and an electric field of, for example, 1 × 10 ⁻⁴ V / cm or more and 1 × 10 ⁷ V / cm or less can be applied between the pair of electrodes. . The electrode in contact with the electron blocking layer is preferably a cathode and the other electrode is preferably an anode.
The elements constituting the photoelectric conversion element according to this embodiment will be described.

(electrode)
The electrodes (upper electrode (transparent conductive film) 15 and lower electrode (conductive film) 11) are made of a conductive material. As the conductive material, a metal, an alloy, a metal oxide, an electrically conductive compound, or a mixture thereof can be used.
Since light is incident from the upper electrode 15, the upper electrode 15 needs to be sufficiently transparent to the light to be detected. Specifically, conductive metal oxides such as tin oxide (ATO, FTO) doped with antimony or fluorine, tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), Metal thin films such as gold, silver, chromium and nickel, and mixtures or laminates of these metals and conductive metal oxides, inorganic conductive materials such as copper iodide and copper sulfide, organic materials such as polyaniline, polythiophene and polypyrrole Examples thereof include conductive materials and laminates of these with ITO. Among these, a transparent conductive metal oxide is preferable from the viewpoint of high conductivity and transparency. The transparent conductive film is preferably formed directly on the photoelectric conversion film. Since the upper electrode 15 is formed on the photoelectric conversion layer 12, it is preferably formed by a method that does not deteriorate the characteristics of the photoelectric conversion layer 12.

  Depending on the application, the lower electrode 11 may have transparency, or conversely, may use a material that does not have transparency and reflects light. Specifically, conductive metal oxides such as tin oxide (ATO, FTO) doped with antimony or fluorine, tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), Metals such as gold, silver, chromium, nickel, titanium, tungsten, and aluminum, and conductive compounds such as oxides and nitrides of these metals (for example, titanium nitride (TiN)), and conductivity with these metals Examples include mixtures or laminates with metal oxides, inorganic conductive materials such as copper iodide and copper sulfide, organic conductive materials such as polyaniline, polythiophene, and polypyrrole, and laminates of these with ITO or titanium nitride. .

The method for forming the electrode is not particularly limited, and can be appropriately selected in consideration of suitability with the electrode material. Specifically, it can be formed by a wet method such as a printing method or a coating method, a physical method such as a vacuum deposition method, a sputtering method, or an ion plating method, or a chemical method such as CVD or plasma CVD method.
When the material of the electrode is ITO, it can be formed by a method such as an electron beam method, a sputtering method, a resistance heating vapor deposition method, a chemical reaction method (such as a sol-gel method), or a dispersion of indium tin oxide. Furthermore, UV-ozone treatment, plasma treatment, or the like can be performed on a film formed using ITO. When the electrode material is TiN, various methods including a reactive sputtering method can be used, and further UV-ozone treatment, plasma treatment, and the like can be performed.
In consideration of the suppression of leakage current, the increase in the resistance value of the thin film, and the increase in transmittance due to the thinning, the thickness of the upper electrode 15 is preferably 5 to 100 nm, more preferably 5 to 20 nm. Things are desirable.

(Photoelectric conversion layer)
In the present invention, the organic material constituting the photoelectric conversion layer (12 in FIG. 1) preferably contains at least one of a p-type organic semiconductor and an n-type organic semiconductor. It is more preferable that both are included. The effect of the present invention is particularly significant when the photoelectric conversion layer contains a material having an electron affinity (Ea) of 4.0 eV or more. Examples of the material having an electron affinity (Ea) of 4.0 eV or more include an n-type organic semiconductor described later.

[P-type organic semiconductor]
A p-type organic semiconductor (compound) is a donor-type 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.
The p-type organic semiconductor is preferably a compound represented by the general formula (I) or (II).

[N-type organic semiconductor]
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 a nitrogen atom, an oxygen atom, or a 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, oxadiazo , Imidazopyridine, pyralidine, pyrrolopyridine, thiadiazolopyridine, dibenzazepine, tribenzazepine, etc.), polyarylene compounds, fluorene compounds, cyclopentadiene compounds, silyl compounds, nitrogen-containing heterocyclic compounds as ligands Etc. 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.

The fullerene, 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.

The photoelectric conversion layer can be formed by vapor deposition. The vapor deposition may be either physical vapor deposition (PVD) or chemical vapor deposition (CVD), but physical vapor deposition such as vacuum vapor deposition is preferred. In the case of forming a film by vacuum vapor deposition, the production conditions such as the degree of vacuum and vapor deposition temperature can be set according to conventional methods.
The thickness of the photoelectric conversion layer is preferably from 10 nm to 1000 nm, more preferably from 50 nm to 800 nm, and particularly preferably from 100 nm to 500 nm. By setting it to 10 nm or more, a suitable dark current suppressing effect is obtained, and by setting it to 1000 nm or less, suitable photoelectric conversion efficiency is obtained.
In the manufacturing method of the photoelectric conversion element of this invention, it is also preferable to include the process which forms a photoelectric converting layer and an electron blocking layer by vacuum heating vapor deposition (vacuum vapor deposition), respectively.

(Electronic blocking layer)
An electron donating organic material can be used for the electron blocking layer. Specifically, in a low molecular material, N, N′-bis (3-methylphenyl)-(1,1′-biphenyl) -4,4′-diamine (TPD) or 4,4′-bis [N Aromatic diamine compounds such as-(naphthyl) -N-phenyl-amino] biphenyl (α-NPD), oxazole, oxadiazole, triazole, imidazole, imidazolone, stilbene derivative, pyrazoline derivative, tetrahydroimidazole, polyarylalkane, butadiene 4,4 ', 4 "tris (N- (3-methylphenyl) N-phenylamino) triphenylamine (m-MTDATA), porphine, tetraphenylporphine copper, phthalocyanine, copper phthalocyanine, titanium phthalocyanine oxide, etc. Compound, triazole derivative, oxazizazole Derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, annealed amine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, silazane derivatives, etc. In the polymer material, polymers such as phenylene vinylene, fluorene, carbazole, indole, pyrene, pyrrole, picoline, thiophene, acetylene, diacetylene, and derivatives thereof can be used. Any compound having an excellent hole transport property can be used.
Specifically, compounds described in [0083] to [0089] of JP-A-2008-72090 are preferable.

[Optical sensor]
Photoelectric conversion elements can be broadly classified into photovoltaic cells and optical sensors, but the photoelectric conversion elements of the present invention are suitable for optical sensors. As an optical sensor, the photoelectric conversion element used alone may be used, or a line sensor in which the photoelectric conversion elements are arranged linearly or a two-dimensional sensor arranged on a plane can be used. The photoelectric conversion element of the present invention converts optical image information into an electrical signal using an optical system and a drive unit like a scanner in a line sensor, and optically converts optical image information like an imaging module in a two-dimensional sensor. The system functions as an image sensor by forming an image on a sensor and converting it into an electrical signal.
Since the photovoltaic cell is a power generation device, the efficiency of converting light energy into electrical energy is an important performance, but the dark current that is a current in a dark place is not a functional problem. Furthermore, a subsequent heating step is not necessary for installing the color filter. Since it is important to convert light and dark signals into electrical signals with high accuracy, the efficiency of converting light intensity into current is also important for optical sensors. Low dark current is required. In addition, resistance to subsequent processes is also important.

[Image sensor]
Next, a configuration example of an image sensor including the photoelectric conversion element of the present invention will be described. In the configuration examples described below, members having the same configuration / action as those already described are denoted by the same or corresponding reference numerals in the drawings, and the description thereof is simplified or omitted.
An image sensor is an element that converts optical information of an image into an electric signal. A plurality of photoelectric conversion elements are arranged on a matrix in the same plane, and an optical signal is converted into an electric signal in each photoelectric conversion element (pixel). That can be output to the outside of the imaging device for each pixel sequentially. Therefore, one pixel is composed of one photoelectric conversion element and one or more transistors.
FIG. 2 is a schematic cross-sectional view showing a schematic configuration of an image sensor for explaining an embodiment of the present invention. This imaging device is used by being mounted on an imaging device such as a digital camera or a digital video camera, an imaging module such as an electronic endoscope or a mobile phone, or the like.

This imaging element has a plurality of photoelectric conversion elements having the configuration shown in FIG. 1 and a circuit board on which a readout circuit for reading a signal corresponding to the charge generated in the photoelectric conversion film of each photoelectric conversion element is formed. A plurality of photoelectric conversion elements are arranged one-dimensionally or two-dimensionally on the same surface above the circuit board.

  2 includes a substrate 101, an insulating layer 102, a connection electrode 103, a pixel electrode (lower electrode) 104, a connection portion 105, a connection portion 106, a photoelectric conversion film 107, and a counter electrode. (Upper electrode) 108, buffer layer 109, sealing layer 110, color filter (CF) 111, partition 112, light shielding layer 113, protective layer 114, counter electrode voltage supply 115, and readout circuit 116.

  The pixel electrode 104 has the same function as the electrode 11 of the photoelectric conversion element 10a illustrated in FIG. The counter electrode 108 has the same function as the electrode 15 of the photoelectric conversion element 10a shown in FIG. The photoelectric conversion film 107 has the same configuration as the layer provided between the electrode 11 and the electrode 15 of the photoelectric conversion element 10a illustrated in FIG.

  The substrate 101 is a glass substrate or a semiconductor substrate such as Si. An insulating layer 102 is formed on the substrate 101. A plurality of pixel electrodes 104 and a plurality of connection electrodes 103 are formed on the surface of the insulating layer 102.

  The photoelectric conversion film 107 is a layer common to all the photoelectric conversion elements provided on the plurality of pixel electrodes 104 so as to cover them.

  The counter electrode 108 is one electrode provided on the photoelectric conversion film 107 and common to all the photoelectric conversion elements. The counter electrode 108 is formed up to the connection electrode 103 disposed outside the photoelectric conversion film 107, and is electrically connected to the connection electrode 103.

  The connection part 106 is embedded in the insulating layer 102 and is a plug or the like for electrically connecting the connection electrode 103 and the counter electrode voltage supply part 115. The counter electrode voltage supply unit 115 is formed on the substrate 101 and applies a predetermined voltage to the counter electrode 108 via the connection unit 106 and the connection electrode 103. When the voltage to be applied to the counter electrode 108 is higher than the power supply voltage of the image sensor, the power supply voltage is boosted by a booster circuit such as a charge pump to supply the predetermined voltage.

  The readout circuit 116 is provided on the substrate 101 corresponding to each of the plurality of pixel electrodes 104, and reads out a signal corresponding to the charge collected by the corresponding pixel electrode 104. The reading circuit 116 is configured by, for example, a CCD, a CMOS circuit, a TFT circuit, or the like, and is shielded from light by a light shielding layer (not shown) disposed in the insulating layer 102. The readout circuit 116 is electrically connected to the corresponding pixel electrode 104 via the connection unit 105.

  The buffer layer 109 is formed on the counter electrode 108 so as to cover the counter electrode 108. The sealing layer 110 is formed on the buffer layer 109 so as to cover the buffer layer 109. The color filter 111 is formed at a position facing each pixel electrode 104 on the sealing layer 110. The partition wall 112 is provided between the color filters 111 and is for improving the light transmission efficiency of the color filter 111.

  The light shielding layer 113 is formed in a region other than the region where the color filter 111 and the partition 112 on the sealing layer 110 are provided, and prevents light from entering the photoelectric conversion film 107 formed outside the effective pixel region. The protective layer 114 is formed on the color filter 111, the partition 112, and the light shielding layer 113, and protects the entire image sensor 100.

  In the imaging device 100 configured as described above, when light is incident, the light is incident on the photoelectric conversion film 107, and charges are generated here. Holes in the generated charges are collected by the pixel electrode 104, and a voltage signal corresponding to the amount is output to the outside of the image sensor 100 by the readout circuit 116.

  The manufacturing method of the image sensor 100 is as follows.

  On the circuit substrate on which the common electrode voltage supply unit 115 and the readout circuit 116 are formed, the connection units 105 and 106, the plurality of connection electrodes 103, the plurality of pixel electrodes 104, and the insulating layer 102 are formed. The plurality of pixel electrodes 104 are arranged on the surface of the insulating layer 102 in a square lattice pattern, for example.

  Next, the photoelectric conversion film 107 is formed on the plurality of pixel electrodes 104 by, for example, a vacuum heating deposition method. Next, the counter electrode 108 is formed on the photoelectric conversion film 107 under vacuum by, for example, sputtering. Next, the buffer layer 109 and the sealing layer 110 are sequentially formed on the counter electrode 108 by, for example, a vacuum heating deposition method. Next, after forming the color filter 111, the partition 112, and the light shielding layer 113, the protective layer 114 is formed, and the imaging element 100 is completed.

  Also in the method of manufacturing the image sensor 100, a step of placing the image sensor 100 being manufactured under non-vacuum is added between the process of forming the photoelectric conversion layer included in the photoelectric conversion film 107 and the process of forming the sealing layer 110. Even so, performance degradation of the plurality of photoelectric conversion elements can be prevented. By adding this step, it is possible to suppress the manufacturing cost while preventing the performance degradation of the image sensor 100.

Below, the detail of the sealing layer 110 of the component of the image pick-up element 100 mentioned above is demonstrated.
[Sealing layer]
The following conditions are required for the sealing layer 110.
First, it is possible to protect the photoelectric conversion layer by preventing intrusion of factors that degrade the organic photoelectric conversion material contained in the solution, plasma, and the like in each manufacturing process of the device.
Secondly, after the device is manufactured, the intrusion of factors such as water molecules that degrade the organic photoelectric conversion material is prevented, and the deterioration of the photoelectric conversion film 107 is prevented over a long period of storage / use.
Third, when the sealing layer 110 is formed, the already formed photoelectric conversion layer is not deteriorated.
Fourth, since incident light reaches the photoelectric conversion film 107 through the sealing layer 110, the sealing layer 110 must be transparent to light having a wavelength detected by the photoelectric conversion film 107.

  The sealing layer 110 can be composed of a thin film made of a single material. However, by providing a multi-layered structure and providing each layer with a different function, stress relaxation of the entire sealing layer 110 and generation of dust during the manufacturing process are possible. Such effects as the suppression of defects such as cracks and pinholes caused by the above, and the optimization of material development can be expected. For example, the sealing layer 110 is formed by laminating a “sealing auxiliary layer” having a function that is difficult to achieve on the layer that serves the original purpose of preventing the penetration of deterioration factors such as water molecules. A two-layer structure can be formed. Although it is possible to have three or more layers, it is preferable that the number of layers is as small as possible in consideration of manufacturing costs.

[Substituent W]
The substituent W is described.
As the substituent W, a halogen atom, an alkyl group (including a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group, an aryl group, and a heterocyclic group (May be referred to as a heterocyclic group), cyano group, hydroxy group, nitro group, carboxy group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, Aryloxycarbonyloxy group, amino group (including anilino group), ammonio group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group Mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and hetero Ring azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, phosphono group, silyl group, hydrazino group, ureido group, boronic acid group (-B (OH) ₂ ), phosphato Examples include a group (—OPO (OH) ₂ ), a sulfato group (—OSO ₃ H), and other known substituents.

More specifically, W represents the following (1) to (48).
(1) Halogen atom For example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom (2) an alkyl group represents a linear, branched, or cyclic substituted or unsubstituted alkyl group. They also include (2-a) to (2-e).
(2-a) alkyl group Preferably an alkyl group having 1 to 30 carbon atoms (for example, methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl) )

(2-b) cycloalkyl group Preferably, the substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms (for example, cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl).
(2-c) Bicycloalkyl group Preferably, the substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms (for example, bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] Octane-3-yl)

(2-d) Tricycloalkyl group Preferably, it is a substituted or unsubstituted tricycloalkyl group having 7 to 30 carbon atoms (for example, 1-adamantyl).

(2-e) A polycyclic cycloalkyl group having a larger ring structure In addition, an alkyl group (for example, an alkyl group of an alkylthio group) in a substituent described below represents an alkyl group of such a concept, Group and alkynyl group.

(3) Alkenyl group represents a linear, branched, or cyclic substituted or unsubstituted alkenyl group. They include (3-a) to (3-c).

(3-a) Alkenyl group Preferably it is a C2-C30 substituted or unsubstituted alkenyl group (for example, vinyl, allyl, prenyl, geranyl, oleyl).

(3-b) Cycloalkenyl group Preferably, the substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms (for example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl)

(3-c) Bicycloalkenyl group A substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms (for example, bicyclo [2,2,1] hept-2-ene -1-yl, bicyclo [2,2,2] oct-2-en-4-yl)

(4) Alkynyl group Preferably, the substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms (for example, ethynyl, propargyl, trimethylsilylethynyl group)

(5) Aryl group Preferably, it is a C6-C30 substituted or unsubstituted aryl group (for example, phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl, ferrocenyl).

(6) Heterocyclic group Preferably, it is a monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, more preferably carbon. It is a 5- or 6-membered aromatic heterocyclic group of 2 to 50. (For example, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl, 2-carbazolyl, 3-carbazolyl, 9-carbazolyl. In addition, like 1-methyl-2-pyridinio and 1-methyl-2-quinolinio A cationic heterocyclic group may be used.)

(7) Cyano group

(8) Hydroxy group

(9) Nitro group

(10) Carboxy group

(11) Alkoxy group Preferably, the substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms (for example, methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy)

(12) Aryloxy group Preferably, it is a C6-C30 substituted or unsubstituted aryloxy group (for example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoyl) Aminophenoxy)

(13) Silyloxy group Preferably, the silyloxy group having 3 to 20 carbon atoms (for example, trimethylsilyloxy, t-butyldimethylsilyloxy)

(14) Heterocyclic oxy group Preferably, the substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms (for example, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy)

(15) Acyloxy group, preferably formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms (for example, formyloxy, acetyloxy , Pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy)

(16) Carbamoyloxy group Preferably, the substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms (for example, N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N- Di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy)

(17) Alkoxycarbonyloxy group Preferably, the substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms (for example, methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy)

(18) Aryloxycarbonyloxy group Preferably, the substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms (for example, phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyl) Oxy)

(19) Amino group Preferably, an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted anilino group having 6 to 30 carbon atoms (for example, amino, methylamino, dimethylamino, Anilino, N-methyl-anilino, diphenylamino)

(20) Ammonio group Preferably, an ammonio group, an ammonio group substituted with 1 to 30 carbon atoms, substituted or unsubstituted alkyl, aryl, or heterocyclic ring (for example, trimethylammonio, triethylammonio, diphenylmethylammonio)

(21) Acylamino group Preferably, a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms (for example, formylamino, acetyl) Amino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino)

(22) Aminocarbonylamino group Preferably, the substituted or unsubstituted aminocarbonylamino having 1 to 30 carbon atoms (for example, carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino) )

(23) Alkoxycarbonylamino group Preferably, the substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms (for example, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N- Methyl-methoxycarbonylamino)

(24) Aryloxycarbonylamino group Preferably, the substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms (for example, phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino) )

(25) Sulfamoylamino group Preferably, the substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms (for example, sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylamino) Sulfonylamino)

(26) Alkyl or arylsulfonylamino group Preferably, the substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, or the substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms (for example, methylsulfonylamino, butylsulfonyl) Amino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino)

(27) Mercapto group

(28) Alkylthio group Preferably, it is a C1-C30 substituted or unsubstituted alkylthio group (for example, methylthio, ethylthio, n-hexadecylthio).

(29) Arylthio group Preferably, the substituted or unsubstituted arylthio having 6 to 30 carbon atoms (for example, phenylthio, p-chlorophenylthio, m-methoxyphenylthio)

(30) Heterocyclic thio group Preferably, the substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms (for example, 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio)

(31) Sulfamoyl group Preferably, the substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms (for example, N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl) N-acetylsulfamoyl, N-benzoylsulfamoyl, N- (N′-phenylcarbamoyl) sulfamoyl)

(32) Sulfo group

(33) an alkyl or arylsulfinyl group, preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms (for example, methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl)

(34) an alkyl or arylsulfonyl group, preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, such as methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl)

(35) Acyl group Preferably, it is a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, a substituted or unsubstituted group having 4 to 30 carbon atoms. Heterocyclic carbonyl groups bonded to carbonyl groups at substituted carbon atoms (eg, acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl )

(36) Aryloxycarbonyl group Preferably, the substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms (for example, phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl) )

(37) Alkoxycarbonyl group Preferably, the substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms (for example, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl)

(38) Carbamoyl group Preferably, the substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms (for example, carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (Methylsulfonyl) carbamoyl)

(39) Aryl and heterocyclic azo group Preferably, the substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, or the substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms (for example, phenylazo, p-chlorophenylazo , 5-ethylthio-1,3,4-thiadiazol-2-ylazo)

(40) Imido group, preferably N-succinimide, N-phthalimide

(41) Phosphino group Preferably, the substituted or unsubstituted phosphino group having 2 to 30 carbon atoms (for example, dimethylphosphino, diphenylphosphino, methylphenoxyphosphino)

(42) Phosphinyl group Preferably, the substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms (for example, phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl).

(43) Phosphinyloxy group Preferably, the substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms (for example, diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy)

(44) Phosphinylamino group Preferably, the substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms (for example, dimethoxyphosphinylamino, dimethylaminophosphinylamino)

(45) Phosphor group

(46) Silyl group Preferably, the substituted or unsubstituted silyl group having 3 to 30 carbon atoms (for example, trimethylsilyl, triethylsilyl, triisopropylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl)
(47) Hydrazino group Preferably a substituted or unsubstituted hydrazino group having 0 to 30 carbon atoms (for example, trimethylhydrazino)
(48) Ureido group Preferably a substituted or unsubstituted ureido group having 0 to 30 carbon atoms (for example, N, N-dimethylureido).

Among the above substituents W, those having a hydrogen atom may be substituted with the above groups by removing this. Examples of such substituents include a —CONHSO ₂ — group (sulfonylcarbamoyl group, carbonylsulfamoyl group), —CONHCO— group (carbonylcarbamoyl group), —SO ₂ NHSO ₂ — group (sulfonylsulfamoyl group). ). More specifically, alkylcarbonylaminosulfonyl group (for example, acetylaminosulfonyl), arylcarbonylaminosulfonyl group (for example, benzoylaminosulfonyl group), alkylsulfonylaminocarbonyl group (for example, methylsulfonylaminocarbonyl), arylsulfonylamino A carbonyl group (for example, p-methylphenylsulfonylaminocarbonyl) is mentioned.

[Ring R]
Examples of the ring R include an aromatic or non-aromatic hydrocarbon ring, a heterocyclic ring, and a polycyclic fused ring formed by further combining these. For example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, triphenylene ring, naphthacene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, Pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenant Examples include a lysine ring, an acridine ring, a phenanthroline ring, a thianthrene ring, a chromene ring, a xanthene ring, a phenoxathiin ring, a phenothiazine ring, and a phenazine ring.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.

[Synthesis of organic materials]
Compounds 1 and 3 shown below were synthesized according to a known method (Japanese Patent Laid-Open No. 2000-297068).
When the decomposition temperatures of the compounds 1 and 3 were measured by simultaneous differential thermothermal gravimetric measurement, the decomposition temperature of the compound 1 was 261 ° C., and the decomposition temperature of the compound 3 was 290 ° C.

[Creation of vapor deposition material]
A material obtained by mixing the compound 3 (organic material) and dimethylacetamide (compound (A)) at the same mass ratio is vacuum-heated and dried for several hours in an atmosphere of 1.0 × 10 ⁻¹ Pa · 200 ° C. By doing so, the vapor deposition material 1 used as the said compound 3 (organic material) 98 mass part and a dimethylacetamide (compound (A)) 2 mass part was created.
A material obtained by mixing the compound 1 (organic material) and dimethylacetamide (compound (A)) at the same mass ratio is vacuum-dried for several hours in an atmosphere of 1.0 × 10 ⁻¹ Pa · 200 ° C. By doing this, the vapor deposition material 1 used as the said compound 1 (organic material) 99 mass parts and a dimethylacetamide (compound (A)) 1 mass part was created.
The boiling point of dimethylacetamide at 1.0 × 10 ⁻¹ Pa is 160 ° C.

Example 1
[Heating of deposition materials and deposition of organic materials]
The vapor deposition material 1 was put into a vacuum vapor deposition apparatus manufactured by ULVAC, and the pressure was set to 7.8 × 10 ⁻⁵ Pa.
While monitoring the degree of vacuum, the dimethylacetamide was heated at a heating rate of about 10 ° C./min up to a boiling point (T ₁ ) of 160 ° C. (T ₂ ) at 1.0 × 10 ⁻¹ Pa at a rate of about 10 ° C./min for a certain period of time. The temperature was maintained (first heating). FIG. 4 shows the temperature and pressure profiles in Example 1. The degree of vacuum temporarily decreased from about 150 ° C., and when heated to 230-240 ° C., the degree of vacuum improved, and the degree of vacuum became higher than at the start. The first heating time was about 30 minutes.
When the degree of vacuum became higher than that at the start, the temperature was raised to 270 ° C., which is the vapor deposition temperature (T ₃ ) of compound 3, which is an organic material (second heating). At this time, a slight deterioration (small change) in the degree of vacuum was observed.
Due to the slight deterioration of the degree of vacuum, the degree of vacuum improved again and became equal to or better than the degree of vacuum before the temperature was raised from 240 ° C. to 270 ° C., and the deposition rate of the compound 3 which is an organic material was 0. After confirming that it reached 5 liters / second, the vapor deposition film forming process was started.
The vapor deposition process was performed continuously for 2 hours to form a 100 nm thick film.
After completion of the vapor deposition film formation process, heating was stopped and the state of the material (residue) in the crucible after cooling to room temperature was examined.

[Measurement of purity]
The purity of compound 3 is determined by HPLC: high performance liquid chromatography for the vapor deposition material before heating, the film 40 minutes after the start of the vapor deposition film formation, the film 100 minutes after the vapor deposition film formation start, and the crucible residue after the vapor deposition is completed. It was measured.

(Example 2)
In Example 1, the vapor deposition material 2 (containing compound 1 and dimethylacetamide) was used in place of the vapor deposition material 1, and the vapor deposition material was heated and the organic material was deposited in the same manner. Evaluated.
The vapor deposition material 2 was put into a vacuum vapor deposition apparatus manufactured by ULVAC, Inc., and the pressure was 7.8 × 10 ⁻⁵ Pa.
While monitoring the degree of vacuum, the temperature was increased to 210 ° C. (T ₂ ) at a rate of temperature increase of about 10 ° C./min, and the temperature was maintained for a certain time (first heating). Changes in temperature and pressure similar to those in Example 1 were observed. The degree of vacuum once decreased from about 150 ° C., and when heated to 200 ° C., the degree of vacuum began to improve, and the degree of vacuum became higher than at the start. The first heating time was about 30 minutes.
When the degree of vacuum became better than at the start, the temperature was raised to 225 ° C., which is the vapor deposition temperature (T ₃ ) of Compound 1 as the organic material (second heating). At this time, a slight deterioration (small change) in the degree of vacuum was observed.
Due to the slight deterioration of the degree of vacuum, the degree of vacuum improved again and became equal to or better than the degree of vacuum before the temperature was raised from 210 ° C. to 225 ° C., and the deposition rate of Compound 1 which is an organic material was 0. After confirming that it reached 5 liters / second, the vapor deposition film forming process was started.
The vapor deposition process was performed continuously for 2 hours to form a 100 nm thick film.
After completion of the vapor deposition film forming process, the heating was stopped and the state of the material (residue) in the crucible after cooling to room temperature was examined.

(Comparative Example 1)
The vapor deposition material 1 was used for vapor deposition by a conventional method. That is, vapor deposition was performed by heating to 270 ° C., which is the vapor deposition temperature of Compound 3, and the purity was similarly evaluated. After the vapor deposition film formation process was finished, heating was stopped and the state of the material (residue) in the crucible after cooling to room temperature was examined. Compound 3 was melted. The temperature and pressure profile of Comparative Example 1 is shown in FIG.

(Comparative Example 2)
In Comparative Example 1, the vapor deposition material 2 (containing compound 1 and dimethylacetamide) was used instead of the vapor deposition material 1, and the vapor deposition material was heated and the organic material was deposited in the same manner. Evaluated.

  As is apparent from the table, the film obtained by the vapor deposition method according to the present invention has a higher purity of the organic material than the film obtained by the conventional method. Moreover, in the vapor deposition method according to the present invention, even an organic material that cannot be sublimated and purified can be continuously deposited with high purity for a long time without being decomposed.

10a, 10b Photoelectric conversion element 11 Lower electrode (conductive thin film)
12 Photoelectric conversion layer (photoelectric conversion film)
15 Upper electrode (transparent conductive thin film)
16A Electron blocking layer 16B Hole blocking layer 100 Image sensor 101 Substrate 102 Insulating layer 103 Connection electrode 104 Pixel electrode (lower electrode)
105 connecting portion 106 connecting portion 107 photoelectric conversion film 108 counter electrode (upper electrode)
109 Buffer layer 110 Sealing layer 111 Color filter (CF)
112 partition wall 113 light shielding layer 114 protective layer 115 counter electrode voltage supply unit 116 readout circuit

Claims (13)

A film obtained by vapor deposition of an organic material that cannot be purified by sublimation purification,
Using a vapor deposition material containing the organic material and a compound (A) having a boiling point or sublimation point T ₁ lower than the vapor deposition temperature T ₃ of the organic material,
The deposition material is heated to a temperature T _{2 that} is higher than the boiling point or sublimation point T ₁ of the compound (A) and lower than the deposition temperature T _{3 of the} organic material by the first heating, and then reaches the temperature T ₂ . Maintain,
After the first heating, the second heating, the deposition temperature T ₃ or more organic materials, after raising the temperature to the decomposition temperature below the temperature of the organic material, a vapor deposited film formation of the organic material was maintained at this temperature A membrane obtained by performing.
Here, the boiling point or sublimation point T ₁ of the compound (A) is the boiling point or sublimation point of the compound (A) at 1.0 × 10 ⁻¹ Pa.
Deposition temperature T ₃ of the organic material refers to the temperature at which the deposition rate of the organic material reaches the 0.5 Å / sec.
The decomposition temperature of an organic material refers to a temperature at which weight loss of 1% or more occurs when the organic material is heated at a constant temperature for 60 minutes in differential thermogravimetry.   The film according to claim 1, wherein the second heating is started after the compound (A) has evaporated or sublimated.   3. The film according to claim 2, wherein the second heating is started after confirming that the compound (A) has evaporated or sublimated according to the value of the degree of vacuum in the film forming chamber.   The film | membrane of any one of Claims 1-3 whose said organic material is an organic material used for formation of a photoelectric converting film. The film according to any one of claims 1 to 4, wherein the organic material is a donor-acceptor type dye compound represented by the following general formula (I).
Formula (I)

(D represents an atomic group having a hetero atom. A represents a group having a carbonyl group or a cyano group. L ₂ and L ₃ each independently represent an unsubstituted methine group or a substituted methine group. N represents 0. (It represents the integer above.) The film according to any one of claims 1 to 5, wherein the organic material is a compound represented by the following general formula (II).
Formula (II)

(In the formula, 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, D ₁ represents an atomic group having a hetero atom, and n represents an integer of 0 or more.) The film according to any one of claims 1 to 6, wherein the compound (A) is an organic solvent having a boiling point of 120 ° C or higher at 1.0 × 10 ^-1 Pa.   The film according to any one of claims 1 to 7, wherein the compound (A) is dimethylacetamide, 1-ethyl-2-pyrrolidone, or N, N-dimethylformamide. The difference between the boiling point or sublimation point _{T 1} of the deposition temperature _{T 3} and the compound of the organic material (A) is a 50 to 160 ° C., film according to any one of claims 1-8. The difference between the _{T 1} and _{T 2} is a 30 to 100 ° C., film according to any one of claims 1-9. The difference between the _{T 2} and _{T 3} are the 10 to 60 ° C., film according to any one of claims 1 to 10.   It is a photoelectric conversion element which has a transparent conductive film, a photoelectric converting film, and a conductive film in this order, Comprising: The said photoelectric converting film is a film | membrane of any one of Claims 1-11, Photoelectric conversion element. A method for producing a film obtained by vapor deposition of an organic material that cannot be purified by sublimation purification,
Using a vapor deposition material containing the organic material and a compound (A) having a boiling point or sublimation point T ₁ lower than the vapor deposition temperature T ₃ of the organic material,
The deposition material is heated to a temperature T _{2 that} is higher than the boiling point or sublimation point T ₁ of the compound (A) and lower than the deposition temperature T _{3 of the} organic material by the first heating, and then reaches the temperature T ₂ . Maintain,
After the first heating, the second heating, the deposition temperature T ₃ or more organic materials, after raising the temperature to the decomposition temperature below the temperature of the organic material, a vapor deposited film formation of the organic material was maintained at this temperature A method for producing a film.
Here, the boiling point or sublimation point T ₁ of the compound (A) is the boiling point or sublimation point of the compound (A) at 1.0 × 10 ⁻¹ Pa.
Deposition temperature T ₃ of the organic material refers to the temperature at which the deposition rate of the organic material reaches the 0.5 Å / sec.
The decomposition temperature of an organic material refers to a temperature at which weight loss of 1% or more occurs when the organic material is heated at a constant temperature for 60 minutes in differential thermogravimetry.

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