JP7236271B2 - p-type organic semiconductor, composition, photoelectric conversion film, photoelectric conversion device, and imaging device - Google Patents

Description

The present invention relates to a p-type organic semiconductor, a composition, a photoelectric conversion film, a photoelectric conversion device, and an imaging device.

Organic semiconductors have a wide variety of variations because their properties can be easily changed by changing their molecular structures. For this reason, organic semiconductors are considered to be capable of realizing functions that cannot be achieved by inorganic semiconductors, and are being actively studied.

2. Description of the Related Art In recent years, the development of imaging devices capable of simultaneously obtaining an image using visible light and an image using near-infrared light is underway. Such an imaging device has a photoelectric conversion element (light receiving element) in which a photoelectric conversion film containing a semiconductor capable of detecting near-infrared light is formed between a pair of electrodes.

Here, in the case of an inorganic semiconductor, it is difficult to design so as to absorb only near-infrared light.

On the other hand, organic semiconductors can be designed to absorb only near-infrared light, so organic semiconductors are used for photoelectric conversion films capable of detecting near-infrared light.

For example, in Patent Document 1, a tin naphthalocyanine derivative is used as a p-type organic semiconductor contained in a photoelectric conversion film capable of detecting near-infrared light.

JP 2016-225456 A

Here, the photoelectric conversion film containing the p-type organic semiconductor of Patent Document 1 can be formed by a resistance heating vapor deposition method. There is a problem of lowering

An object of one embodiment of the present invention is to provide a p-type organic semiconductor that has excellent heat resistance and is capable of detecting near-infrared light.

One aspect of the present invention is a p-type organic semiconductor represented by general formula (1)

［式中、Ｒ_１、Ｒ_２は、それぞれ独立に、置換もしくは無置換の炭素数１～３０のアルキル基であり、Ｒ_３～Ｒ_２６は、それぞれ独立に、水素原子、重水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基、置換もしくは無置換のアルコキシ基、置換もしくは無置換のアルキルチオ基、置換もしくは無置換のアリールオキシ基、置換もしくは無置換のアリールチオ基、置換もしくは無置換の複素環基で置換されたオキシ基、置換もしくは無置換の複素環基で置換されたチオ基、または、置換もしくは無置換のアミノ基である。］
で表される。

[In the formula, R ₁ and R ₂ are each independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and R ₃ to R ₂₆ are each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted aryloxy group, substituted or unsubstituted arylthio group, substituted or unsubstituted It is an oxy group substituted with an unsubstituted heterocyclic group, a thio group substituted with a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted amino group. ]
is represented by

According to one aspect of the present invention, it is possible to provide a p-type organic semiconductor that has excellent heat resistance and is capable of detecting near-infrared light.

It is a schematic sectional drawing which shows an example of the photoelectric conversion element of this embodiment. FIG. 3 is a schematic cross-sectional view showing another example of the photoelectric conversion element of this embodiment; 1 is a schematic cross-sectional view showing a first example of an imaging device of this embodiment; FIG. It is a schematic sectional drawing which shows the second example of the image pick-up element of this embodiment. It is a schematic sectional drawing which shows the 3rd example of the imaging device of this embodiment. It is a schematic perspective view which shows the 3rd example of the image pick-up element of this embodiment. It is a schematic sectional drawing which shows the 4th example of the image pick-up element of this embodiment. It is a schematic sectional drawing which shows the 5th example of the imaging device of this embodiment. It is a schematic perspective view which shows the fifth example of the image pick-up element of this embodiment.

Next, the form for implementing this invention is demonstrated.

In the following drawings, the thicknesses are shown enlarged in order to clearly express a plurality of layers and regions. In addition, in the drawings, in order to clearly describe the present embodiment, unnecessary parts for the description are omitted. Further, the same reference numerals are used throughout the specification to refer to the same or similar components.

In addition, when a certain part such as a layer, film, region, plate, etc. is “above” another part, a case where a certain part is “directly above” another part, and a case where one part and another part are Including the case where there is another part between them. Conversely, when a portion is said to be "directly on" another portion, it means that there is no further portion between that portion and the other portion.

[p-type organic semiconductor]
The p-type organic semiconductor of this embodiment has the general formula (1)

［式中、Ｒ_１、Ｒ_２は、それぞれ独立に、置換もしくは無置換の炭素数１～３０のアルキル基であり、Ｒ_３～Ｒ_２６は、それぞれ独立に、水素原子、重水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基、置換もしくは無置換のアルコキシ基、置換もしくは無置換のアルキルチオ基、置換もしくは無置換のアリールオキシ基、置換もしくは無置換のアリールチオ基、置換もしくは無置換の複素環基で置換されたオキシ基、置換もしくは無置換の複素環基で置換されたチオ基、または、置換もしくは無置換のアミノ基である。］
で表される。

[In the formula, R ₁ and R ₂ are each independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and R ₃ to R ₂₆ are each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted aryloxy group, substituted or unsubstituted arylthio group, substituted or unsubstituted It is an oxy group substituted with an unsubstituted heterocyclic group, a thio group substituted with a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted amino group. ]
is represented by

Since the p-type organic semiconductor of this embodiment is a tin naphthalocyanine derivative, it can detect near-infrared light.

In addition, the p-type organic semiconductor of the present embodiment has R ₁ and R ₂ as axial substituents of the tin naphthalocyanine derivative, and is therefore excellent in heat resistance. Therefore, even if a photoelectric conversion film containing the p-type organic semiconductor of this embodiment is formed by a resistance heating vapor deposition method, thermal deterioration of the p-type organic semiconductor of this embodiment can be suppressed. The conversion efficiency of the photoelectric conversion element is improved.

The alkyl groups for R ₃ to R ₂₆ are linear, branched or cyclic alkyl groups.

Examples of linear alkyl groups include methyl, ethyl, propyl, butyl, octyl, decyl, and pentadecyl groups.

Examples of branched alkyl groups include t-butyl groups.

Cyclic alkyl groups include, for example, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl groups.

The number of carbon atoms in the linear or branched alkyl group is preferably 1-20, more preferably 1-10.

The number of carbon atoms in the cyclic alkyl group is preferably 3-20, more preferably 3-12.

The aryl groups for R ₃ to R ₂₆ are monocyclic, non-fused polycyclic or condensed polycyclic aryl groups.

Monocyclic aryl groups include, for example, a phenyl group.

Non-fused polycyclic aryl groups include, for example, a biphenyl group, a terphenyl group, a quaterphenyl group, a kinkphenyl group, a sexiphenyl group, a fluoranthenyl group, and a triphenylenyl group.

Condensed polycyclic aryl groups include, for example, naphthyl group, anthryl group, phenanthryl group, fluorenyl group, indenyl group, pyrenyl group, acetonaphthenyl group, bisphenylfluorenyl group, 9-(9-fluorenyl)fluorenyl group and the like. are mentioned.

The number of ring-forming carbon atoms in the monocyclic, non-condensed polycyclic or condensed polycyclic aryl group is preferably 6-50, more preferably 6-40.

The alkyl groups in the alkoxy groups and alkylthio groups of R ₃ to R ₂₆ are the same as the alkyl groups described above.

The aryl groups in the aryloxy groups and arylthio groups of R ₃ to R ₂₆ are the same as the aryl groups described above.

The heterocyclic group in the oxy group substituted with a heterocyclic group for R ₃ to R ₂₆ and the thio group substituted with a substituted or unsubstituted heterocyclic group is a monocyclic or polycyclic heterocyclic group.

Examples of monocyclic heterocyclic groups include pyrrolyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, furanyl, pyranyl, thienyl, pyridyl, pyrazyl, and pyrimidinyl groups. , a pyridazinyl group, a triazinyl group, a quinolyl group, an isoquinolyl group, and the like.

Examples of polycyclic heterocyclic groups include benzo(pyridyl)furanyl, benzofuranyl, benzothienyl, indolyl, carbazolyl, carbolinyl, phenanthridinyl, acridinyl, perimidinyl, phenanthroli nil group, benzoxazolyl group, benzothiazolyl group, quinoxalyl group, benzimidazolyl group, pyrazolyl group, dibenzofuranyl group, dibenzothienyl group and the like.

The number of ring-forming carbon atoms in the monocyclic or polycyclic heterocyclic group is preferably 5-50, more preferably 5-30.

Among these, R ₃ to R ₂₆ are each independently preferably a hydrogen atom or a deuterium atom. This can further improve the heat resistance of the p-type organic semiconductor.

Examples of substituents for R ₁ to R ₂₆ include a cyano group, a silyl group, a monoalkylsilyl group having 1 to 10 carbon atoms, a dialkylsilyl group or a trialkylsilyl group, and a linear or branched group having 1 to 10 carbon atoms. linear or cyclic alkyl groups, linear or branched alkoxy groups having 1 to 10 carbon atoms, aryl groups having 6 to 15 ring carbon atoms, aryloxy groups having 6 to 15 ring carbon atoms, and ring carbon atoms arylcarbonyl group having 6 to 15 carbon atoms, heterocyclyl group having 3 to 32 ring carbon atoms, monoalkylamino group or dialkylamino group having 1 to 10 carbon atoms, monoarylamino group or diarylamino group having 6 to 15 ring carbon atoms etc.

In the general formula (1), when R ₃ to R ₂₆ are electron-withdrawing groups such as halogen atoms (e.g., F, Cl), it becomes an n-type organic semiconductor (e.g., JP-A-2009-218369 reference).

The p-type organic semiconductor of this embodiment has the general formula (2)

［式中、ｎ_１、ｎ_２は、それぞれ独立に、０～１０の整数であり、Ｙ_１～Ｙ_６は、それぞれ独立に、直鎖アルキル基であり、Ｒ_２７～Ｒ_３０は、それぞれ独立に、水素原子または重水素原子である。］
で表されることが好ましい。これにより、ｐ型有機半導体の熱耐性をさらに向上させることができる。

[wherein n ₁ and n ₂ are each independently an integer of 0 to 10, Y ₁ to Y ₆ are each independently a linear alkyl group, and R ₂₇ to R ₃₀ are each independently is a hydrogen atom or a deuterium atom. ]
is preferably represented by This can further improve the heat resistance of the p-type organic semiconductor.

[Composition]
The composition of this embodiment contains the p-type organic semiconductor of this embodiment and an n-type organic semiconductor. A photoelectric conversion film can be formed by using the composition of the present embodiment.

The n-type organic semiconductor is not particularly limited as long as it can form a pn junction with the p-type organic semiconductor of the present embodiment, but examples thereof include subphthalocyanine, fullerene and its derivatives, thiophene and its derivatives. , may be used in combination of two or more. Among these, fullerenes and/or fullerene derivatives are preferable from the viewpoint of the conversion efficiency of the photoelectric conversion film.

Fullerenes include, for example, C50, C60, C70, C76, C78, C80, C82, C84, C90, C96, C240 and C540.

Derivatives of fullerene are those in which the fullerene is substituted with a substituent.

Examples of substituents include the aforementioned alkyl groups, aryl groups, and heterocyclic groups.

[Photoelectric conversion element]
FIG. 1 shows an example of the photoelectric conversion element of this embodiment.

A photoelectric conversion element 100 has an (organic) photoelectric conversion film 30 formed between a first electrode 10 and a second electrode 20 facing each other.

At least one of the first electrode 10 and the second electrode 20 is a translucent electrode capable of transmitting near-infrared light.

Examples of materials forming the translucent electrode include conductive materials such as indium tin oxide (ITO), indium zinc oxide (IZO), AZO, FTO, SnO ₂ , TiO ₂ and ZnO ₂ .

The translucent electrode may be formed of a single layer, or may be a laminate of multiple layers.

When the first electrode 10 or the second electrode 20 is an opaque electrode that does not transmit near-infrared light, examples of materials that constitute the opaque electrode include aluminum (Al), copper, gold, and silver. and conductive materials such as polysilicon imparted with conductivity by being doped with impurities.

Various methods can be applied to form the first electrode 10 and the second electrode 20 depending on the materials used.

For example, when forming an ITO electrode, 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 method of applying an indium tin oxide dispersion can be applied. can.

Further, when forming the first electrode 10 and the second electrode 20, UV-ozone treatment, plasma treatment, or the like may be performed.

Here, the first electrode 10 is an electrode that collects holes among charges generated in the photoelectric conversion film 30 . Also, the second electrode 20 is an electrode that collects electrons among the charges generated in the photoelectric conversion film 30 .

By applying a bias voltage between the first electrode 10 and the second electrode 20, among charges generated in the photoelectric conversion film 30, holes are moved to the first electrode 10, and electrons are transferred to the second electrode. can be moved to the electrode 20 of

Here, when the photoelectric conversion device 100 is applied to an imaging device, which will be described later, it is converted into a voltage signal according to the amount of holes that have moved to the first electrode 10 and read out. Thereby, the near-infrared light can be converted into a voltage signal and taken out.

A bias voltage may be applied so that the first electrode 10 collects electrons and the second electrode 20 collects holes.

The photoelectric conversion film 30 includes the p-type organic semiconductor of this embodiment and an n-type organic semiconductor, and is a film in which the p-type organic semiconductor of this embodiment and the n-type organic semiconductor form a pn junction. When the photoelectric conversion film 30 receives near-infrared light, excitons are generated. After the excitons are separated into holes and electrons, the holes migrate to the first electrode 10 and the electrons migrate to the second electrode 20 , resulting in current flow in the photoelectric conversion element 100 .

The n-type organic semiconductor is the same as the n-type organic semiconductor contained in the composition of this embodiment.

The photoelectric conversion film 30 may be formed of a single layer, or may be laminated with a plurality of layers.

The photoelectric conversion film 30 formed of a single layer includes an intrinsic semiconductor layer.

Examples of the laminated structure of the photoelectric conversion film 30 in which a plurality of layers are laminated include: p-type semiconductor layer/intrinsic semiconductor layer, intrinsic semiconductor layer/n-type semiconductor layer, p-type semiconductor layer/intrinsic semiconductor layer/n-type semiconductor layer, p-type semiconductor layer/n-type semiconductor layer, and the like.

The intrinsic semiconductor layer includes the p-type organic semiconductor of this embodiment and the n-type organic semiconductor.

The volume ratio of the n-type organic semiconductor to the p-type organic semiconductor of this embodiment in the intrinsic semiconductor layer is preferably 0.01-100, more preferably 0.02-95. Thereby, the conversion efficiency of the photoelectric conversion film 30 can be further improved.

The p-type semiconductor layer contains the p-type organic semiconductor of this embodiment.

The n-type semiconductor layer includes an n-type organic semiconductor.

The thickness of the photoelectric conversion film 30 is preferably 1 nm to 800 nm, more preferably 5 nm to 500 nm. Thereby, the conversion efficiency of the photoelectric conversion film 30 can be further improved.

The photoelectric conversion film 30 is preferably formed by a dry film formation method, more preferably by a resistance heating vapor deposition method, but may be formed by a wet film formation method.

Examples of the dry film forming method include a vacuum vapor deposition method.

Specific examples of the vacuum vapor deposition method include an electron beam method, a sputtering method, and a resistance heating vapor deposition method.

Examples of the wet film forming method include a solution coating method.

Specific examples of solution coating methods include casting, spin coating, dip coating, blade coating, wire bar coating, spray coating, inkjet printing, screen printing, offset printing, letterpress printing, and the like. mentioned.

Specific examples of the patterning method when the photoelectric conversion film 30 needs to be patterned include a resist etching method, a laser removal method, and the like.

FIG. 2 shows another example of the photoelectric conversion element of this embodiment.

The photoelectric conversion element 200 has an electron blocking layer 40 and a hole blocking layer 45 formed between the first electrode 10 and the photoelectric conversion film 30 and between the second electrode 20 and the photoelectric conversion film 30, respectively. is the same as the photoelectric conversion element 100 except that

The electron blocking layer 40 suppresses injection of electrons from the first electrode 10 to the photoelectric conversion film 30 and also prevents electrons generated in the photoelectric conversion film 30 from moving to the first electrode 10 .

The hole blocking layer 45 prevents holes from being injected into the photoelectric conversion film 30 from the second electrode 20 and prevents holes generated in the photoelectric conversion film 30 from moving to the second electrode 20 . impede.

Materials constituting the electron blocking layer 40 include, for example, poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), polyarylamine, poly(N-vinylcarbazole), polyaniline, Polypyrrole, N,N,N',N'-tetrakis(4-methoxyphenyl)benzidine (TPD), 4,4'-bis[N-(1-naphthyl)-N-phenyl-amino]biphenyl (α-NPD ), m-MTDATA, 4,4′,4″-tris(N-carbazolyl)triphenylamine (TCTA) and the like, and two or more of them may be used in combination.

Examples of materials constituting the hole blocking layer 45 include naphthalene-1,4,5,8-tetracarboxylic dianhydride (NTCDA), bathocuproine (BCP), LiF, Alq3, Gaq3, Inq3, Znq2, and Zn. (BTZ)2, BeBq2, etc. may be mentioned, and two or more of them may be used in combination.

Note that the electron blocking layer 40 or the hole blocking layer 45 may be omitted.

Alternatively, a bias voltage may be applied so that the first electrode 10 collects electrons and the second electrode 20 collects holes. In this case, hole blocking layer 40 and electron blocking layer 45 may be formed instead of electron blocking layer 40 and hole blocking layer 45, respectively.

The photoelectric conversion device of the present embodiment can be applied to imaging devices, solar cells, photodetectors, photosensors, photodiodes, and the like.

[Image sensor]
FIG. 3 shows an example of the imaging element of this embodiment.

The imaging element 300 includes a semiconductor substrate 310 , an insulating layer 80 and a photoelectric conversion element 100 .

Semiconductor substrate 310 is a silicon substrate on which the transfer transistor and charge storage location 55 are integrated. Here, the transfer transistor and the charge storage location 55 are integrated for each pixel, the charge storage location 55 is electrically connected to the photoelectric conversion element 100, and the information in the charge storage location 55 is stored in the transmission transistor. forwarded by

Metal wiring and pads are provided on the semiconductor substrate 310 .

The material constituting the metal wiring and pad is not particularly limited as long as it can reduce the signal delay, but for example, aluminum (Al), copper (Cu), silver (g), alloys thereof), etc. metals with low resistivity.

An insulating layer 80 is formed on the semiconductor substrate 310 on which the metal wiring and pads are formed.

Examples of the material forming the insulating layer 80 include inorganic insulating substances such as silicon oxide and silicon nitride, and materials with low dielectric constants (Low-k materials) such as SiC, SiCOH, SiCO, and SiOF.

The insulating layer 80 is formed with a contact hole for exposing the pad and a through hole 85 for exposing the charge storage location 55 of each pixel.

A photoelectric conversion element 100 is formed on the insulating layer 80 .

As described above, the photoelectric conversion element 100 includes the first electrode 10, the photoelectric conversion film 30, and the second electrode 20. The second electrode 20 can transmit near-infrared light. It is a transparent electrode. Therefore, when light including near-infrared light is incident from the second electrode 20 side, the near-infrared light is absorbed and photoelectrically converted by the photoelectric conversion film 30 .

A band-pass filter that transmits only near-infrared light may be provided above the photoelectric conversion element 100 .

FIG. 4 shows a second example of the imaging device of this embodiment.

The imaging element 400 has the same configuration as the imaging element 300 except that the photoelectric conversion element 200 is applied instead of the photoelectric conversion element 100 .

5 and 6 show a third example of the imaging element of this embodiment.

The imaging element 500 includes a semiconductor substrate 310 , a lower insulating layer 60 , a color filter layer 70 , an upper insulating layer 80 and a photoelectric conversion element 100 .

The semiconductor substrate 310 is a silicon substrate on which the photosensitive elements (50G, 50B, 50R), transmission transistors and charge storage locations 55 are integrated. Here, the photosensitive elements (50G, 50R, 50B) are silicon photodiodes. Also, the photosensitive elements (50G, 50B, 50R), the transfer transistors, and the charge storage location 55 are integrated for each pixel, and the photosensitive elements (50G, 50B, 50R) correspond to the green pixel, blue pixel and red pixel, respectively. Included in the pixel, charge storage location 55 is included in the near-infrared pixel.

The photosensitive elements (50G, 50B, 50R) sense green light, blue light and red light respectively, and the sensed information is transferred by transmission transistors. Also, the charge storage location 55 is electrically connected to the photoelectric conversion element 100, and the information in the charge storage location 55 is transferred by the transmission transistor.

Although metal wiring and pads are provided on the semiconductor substrate 310, the metal wiring and pads may be provided below the photosensitive elements (50G, 50B, 50R).

A lower insulating layer 60 is formed on the semiconductor substrate 310 on which the metal wires and pads are formed.

As the material forming the lower insulating layer 60, the same material as the material forming the insulating layer 80 can be used.

A color filter layer 70 is formed on the lower insulating layer 60 .

The color filter layer 70 includes blue filters 70B formed in blue pixels, green filters 70G formed in green pixels, and red filters 70R formed in red pixels.

An upper insulating layer 80 is formed on the color filter layer 70 in order to remove steps due to the color filter layer 70 and planarize.

The upper insulating layer 80 and the lower insulating layer 60 are formed with contact holes for exposing the pads and through holes 85 for exposing the charge storage locations 55 .

A photoelectric conversion element 100 is formed on the upper insulating layer 80 .

The photoelectric conversion element 100 includes the first electrode 10, the photoelectric conversion film 30, and the second electrode 20, as described above. Here, the first electrode 10 is a translucent electrode capable of transmitting near-infrared light and visible light. Also, the second electrode 20 is a translucent electrode capable of transmitting visible light. Therefore, when light including near-infrared light and visible light is incident from the second electrode 20 side, the near-infrared light is absorbed and photoelectrically converted by the photoelectric conversion film 30 . On the other hand, the light not absorbed by the photoelectric conversion film 30 is sensed by the photosensitive elements (50G, 50B, 50R) after passing through the first electrode 10 and the color filter layer 70. FIG.

A band-pass filter that transmits only visible light and near-infrared light may be provided above the photoelectric conversion element 100 .

FIG. 7 shows a fourth example of the imaging device of this embodiment.

The imaging element 600 has the same configuration as the imaging element 500 except that the photoelectric conversion element 200 is applied instead of the photoelectric conversion element 100 .

8 and 9 show a fifth example of the imaging element of this embodiment.

The imaging element 700 includes a semiconductor substrate 310, an insulating layer 80, and a photoelectric conversion element 100, similar to the imaging element 500. The semiconductor substrate 310 includes photosensitive elements (50G, 50B, 50R), transmission transistors, and charge transfer elements. Storage locations 55 are integrated.

However, unlike the image sensor 500, the image sensor 700 has the photosensitive elements 50B, 50G and 50R laminated, and the color filter layer 70 is omitted.

Photosensitive elements 50B, 50G and 50R are electrically connected to charge storage locations, and information in the charge storage locations is transferred by transmission transistors.

Photosensitive elements 50B, 50G and 50R can selectively absorb blue, green and red light, respectively, depending on the stacking depth.

Since the photoelectric conversion element 100 and the photosensitive elements 50B, 50G, and 50R are stacked, the imaging element 700 can be miniaturized.

Note that organic photoelectric conversion elements capable of selectively absorbing green light, blue light and red light may be used instead of the photosensitive elements (50G, 50B, 50R). As a result, the sensitivity of the imaging element is improved, and crosstalk can be reduced.

In this case, the order of stacking the photoelectric conversion element 100 and the organic photoelectric conversion element capable of selectively absorbing green light, blue light and red light is not particularly limited.

Also, the photoelectric conversion element 200 may be applied instead of the photoelectric conversion element 100 .

The imaging device of this embodiment can be applied to various electronic devices such as mobile phones and digital cameras.

Examples of the present invention are described below. However, the technical scope of the present invention is not limited only to the following examples.

[Example 1]
1,3-Diiminobenz[f]isoindoline (2.0 g) (manufactured by Tokyo Kasei) and Di-t-butyltin dichloride (1.5 g) (manufactured by Aldrich) were stirred in 1-Chloronaphthalene under reflux for 2 hours. , the reaction mixture was allowed to reach room temperature. Next, after filtering a deposit, it wash|cleaned by chloroform, a pyridine, and methanol, and obtained the compound 1 (1.5g) as a p-type organic semiconductor.

［比較例１］
ｐ型有機半導体として、スズナフタロシアニン（Ａｌｄｒｉｃｈ製）を用いた。

[Comparative Example 1]
Tin naphthalocyanine (manufactured by Aldrich) was used as the p-type organic semiconductor.

[Heat resistance of p-type organic semiconductor]
Using TG-DTA, the heat resistance of the p-type organic semiconductor was evaluated by measuring the temperature at which the weight loss was 2% and 5%.

Table 1 shows the evaluation results of the heat resistance of p-type organic semiconductors.

表１から、実施例１のｐ型有機半導体は、熱耐性に高いことがわかる。

Table 1 shows that the p-type organic semiconductor of Example 1 has high heat resistance.

On the other hand, the p-type organic semiconductor of Comparative Example 1 has low heat resistance because the tin naphthalocyanine axial substituent is not introduced.

[Example 2]
On a glass substrate with ITO (thickness 150 nm), the chemical formula

で表される化合物Ａを成膜して、電子ブロッキング層を形成した。次に、抵抗加熱蒸着法により、実施例１のｐ型有機半導体と、ｎ型有機半導体としての、フラーレンＣ６０を、体積比が１：１、膜厚が１５０ｎｍとなるように成膜して、光電変換膜を形成した。さらに、高周波マグネトロンスパッタ法により、膜厚が１０ｎｍとなるようにＩＴＯ膜を成膜して、光電変換素子を得た。

A film of compound A represented by was formed to form an electron blocking layer. Next, the p-type organic semiconductor of Example 1 and fullerene C60 as an n-type organic semiconductor were deposited by a resistance heating vapor deposition method so as to have a volume ratio of 1:1 and a film thickness of 150 nm. A photoelectric conversion film was formed. Further, an ITO film was formed to a thickness of 10 nm by a high-frequency magnetron sputtering method to obtain a photoelectric conversion element.

The degree of vacuum in the above vacuum process was set to 4×10 ⁻⁴ Pa or less.

[Comparative Example 2]
A photoelectric conversion device was obtained in the same manner as in Example 2, except that the p-type organic semiconductor of Comparative Example 1 was used instead of the p-type organic semiconductor of Example 1.

[IPCE of photoelectric conversion element]
After transporting the photoelectric conversion element to a glove box in which the concentrations of moisture and oxygen are each kept at 1 ppm or less without exposing it to the atmosphere, it is sealed in a glass can sealed with a moisture absorbent using a UV curable resin. Sealed.

An IPCE measurement system (manufactured by Mac Science) was used to measure the external quantum efficiency (IPCE) at the maximum conversion efficiency at wavelengths of 810 nm and 940 nm with a negative bias of 3 V applied to the lower electrode of the photoelectric conversion element.

Table 2 shows the IPCE evaluation results of the photoelectric conversion elements.

表２から、実施例２の光電変換素子は、波長８１０ｎｍおよび９４０ｎｍのいずれにおいても、ＩＰＣＥが高いことがわかる。

From Table 2, it can be seen that the photoelectric conversion element of Example 2 has high IPCE at both wavelengths of 810 nm and 940 nm.

On the other hand, the photoelectric conversion element of Comparative Example 2 contains the p-type organic semiconductor of Comparative Example 1, and therefore has a low IPCE. It is considered that this is because the p-type organic semiconductor of Comparative Example 1 was thermally deteriorated when the photoelectric conversion film was formed by the resistance heating vapor deposition method.

10 first electrode 20 second electrode 30 photoelectric conversion film 100, 200 photoelectric conversion element 300, 400, 500, 600, 700 imaging element

Claims (9)

General formula (1)

[In the formula, R ₁ and R ₂ are each independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and R ₃ to R ₂₆ are each independently a hydrogen atom, a deuterium atom, a substituted Or an oxy group substituted with an unsubstituted alkyl group, a substituted or unsubstituted aryl group , a substituted or unsubstituted alkylthio group , a substituted or unsubstituted arylthio group, a substituted or unsubstituted heterocyclic group, a substituted or A thio group substituted with an unsubstituted heterocyclic group, or a substituted or unsubstituted amino group. ]
A p-type organic semiconductor represented by general formula (2)

[wherein n ₁ and n ₂ are each independently an integer of 0 to 10, Y ₁ to Y ₆ are each independently a linear alkyl group, and R ₂₇ to R ₃₀ are each independently is a hydrogen atom or a deuterium atom. ]
The p-type organic semiconductor according to claim 1, represented by: 3. The p-type organic semiconductor according to claim 1, wherein said R ₃ to R ₂₆ are each independently a hydrogen atom or a deuterium atom. The p-type organic semiconductor according to any one of claims 1 to 3,
A composition comprising an n-type organic semiconductor. 5. The composition of claim 4, wherein the n-type organic semiconductor is a fullerene and/or a fullerene derivative. The p-type organic semiconductor according to any one of claims 1 to 3,
A photoelectric conversion film containing an n-type organic semiconductor. A method for producing the photoelectric conversion film according to claim 6, wherein the method comprises forming the p-type organic semiconductor and the n-type organic semiconductor according to any one of claims 1 to 3 by a vacuum deposition method. A method comprising : A photoelectric conversion device comprising the photoelectric conversion film according to claim 6 . An imaging device comprising the photoelectric conversion device according to claim 8 .

Images