JPH07211958A - Formation of phthalocyanine film - Google Patents
Formation of phthalocyanine filmInfo
- Publication number
- JPH07211958A JPH07211958A JP6001772A JP177294A JPH07211958A JP H07211958 A JPH07211958 A JP H07211958A JP 6001772 A JP6001772 A JP 6001772A JP 177294 A JP177294 A JP 177294A JP H07211958 A JPH07211958 A JP H07211958A
- Authority
- JP
- Japan
- Prior art keywords
- phthalocyanine
- film
- substrate
- type crystal
- raw material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 230000015572 biosynthetic process Effects 0.000 title description 7
- 239000013078 crystal Substances 0.000 claims abstract description 110
- 239000000758 substrate Substances 0.000 claims abstract description 92
- 239000002994 raw material Substances 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 42
- 238000001704 evaporation Methods 0.000 claims abstract description 17
- 238000010894 electron beam technology Methods 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims description 4
- 230000000052 comparative effect Effects 0.000 description 20
- 238000007740 vapor deposition Methods 0.000 description 16
- 238000000862 absorption spectrum Methods 0.000 description 15
- 239000010949 copper Substances 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 13
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 13
- 230000008020 evaporation Effects 0.000 description 11
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 108091008695 photoreceptors Proteins 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Photoreceptors In Electrophotography (AREA)
- Light Receiving Elements (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、フタロシアニン膜の成
膜方法に関し、更に詳しくはコピー機等の電子写真感光
体の材料に用いられるフタロシアニン膜の成膜方法に関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a phthalocyanine film, and more particularly to a method for forming a phthalocyanine film used as a material for an electrophotographic photoreceptor such as a copying machine.
【０００２】[0002]
【従来の技術】従来、この種の電子写真感光体の構成と
しては図２（Ａ，Ｂ，Ｃ，Ｄ）に示すものが知られてい
る。2. Description of the Related Art Conventionally, as a structure of this type of electrophotographic photosensitive member, one shown in FIG. 2 (A, B, C, D) is known.
【０００３】また、図２に示す構成のうち、構成Ｃおよ
びＤの電荷発生層３の成膜方法としては、フタロシアニ
ン原料を蒸発源の抵抗加熱により加熱して蒸発させて基
板上に蒸着させて成膜する蒸着法、或いは他の層と同様
にフタロシアニンの溶液中に浸漬して付着させて成膜す
る浸漬法が用いられていた。In the method of forming the charge generation layer 3 of the configurations C and D in the configuration shown in FIG. 2, a phthalocyanine raw material is heated by resistance heating of an evaporation source to evaporate it and deposit it on a substrate. A vapor deposition method for forming a film, or a dipping method for forming a film by immersing it in a solution of phthalocyanine and adhering it in the same manner as other layers has been used.
【０００４】そして、フタロシアニンの工業的に最も重
要な結晶系はα型結晶とβ型結晶であり、フタロシアニ
ンは一般には略してＭＰｃと称している。ＭはＨ2，Ｂ
ｅ，Ｍｎ，Ｆｅ，Ｃｏ，Ｎｉ，Ｃｕ，Ｐｔ等の金属を示
し、また、Ｐｃはフタロシアニンを示す。The industrially most important crystal system of phthalocyanine is α type crystal and β type crystal, and phthalocyanine is generally abbreviated as MPc. M is H 2 , B
Metals such as e, Mn, Fe, Co, Ni, Cu and Pt are shown, and Pc is phthalocyanine.
【０００５】また、β型結晶は結晶系の中でも熱力学的
に最も安定な構造であり、また、α型結晶は不安定な構
造である。その他の結晶系としてはα型結晶とβ型結晶
との間にγ型結晶、ε型結晶、δ型結晶、π型結晶、ρ
型結晶、χ型結晶、Ｒ型結晶が知られているが、いずれ
も準安定型である。The β-type crystal has the most thermodynamically stable structure among crystal systems, and the α-type crystal has an unstable structure. Other crystal systems include γ-type crystals, ε-type crystals, δ-type crystals, π-type crystals, ρ between α-type crystals and β-type crystals.
Type crystals, χ type crystals, and R type crystals are known, but all are metastable types.
【０００６】ＭＰｃのうちＨ2・Ｐｃ（無金属フタロシ
アニン）とＣｕ・Ｐｃ（銅フタロシアニン）は電子写真
の感光体に利用されている。Of MPc, H 2 .Pc (metal-free phthalocyanine) and Cu.Pc (copper phthalocyanine) are used for electrophotographic photoreceptors.
【０００７】また、これらの電子写真感光体の光導電性
は結晶の軸方向によりキャリヤの生成効率や移動度が異
なり、特にβ型結晶が電荷の載り、光導電性ともα型結
晶より優れている。また、Ｈ2・Ｐｃのχ型結晶、Ｃｕ
・Ｐｃのε型結晶はＨ2・Ｐｃ、Ｃｕ・Ｐｃのβ型結晶
よりも電荷の載り、光導電性が優れている。しかし、こ
のχ型結晶、或いはε型結晶は準安定型であるため、工
業的には一般に安定なβ型結晶が使用されている。Further, the photoconductivity of these electrophotographic photosensitive members is different in carrier generation efficiency and mobility depending on the axial direction of the crystal, and in particular, β-type crystals carry an electric charge and are superior in photoconductivity to α-type crystals. There is. In addition, χ type crystal of H 2 · Pc, Cu
The ε-type crystal of Pc has a higher charge and has better photoconductivity than the β-type crystal of H 2 · Pc and Cu · Pc. However, since the χ type crystal or the ε type crystal is a metastable type, a stable β type crystal is generally used industrially.
【０００８】[0008]
【発明が解決しようとする課題】前記フタロシアニン膜
の成膜方法のうち、蒸着法は浸漬法に比して、膜厚の均
一性、成膜の制御性の点で優れているが、しかし基板上
に成膜されたフタロシアニン膜はα型結晶である。Among the above-mentioned phthalocyanine film forming methods, the vapor deposition method is superior to the dipping method in the uniformity of the film thickness and the controllability of the film formation. The phthalocyanine film formed above is an α-type crystal.
【０００９】このため、電子写真感光体として使用する
ため基板上に成膜されたフタロシアニン膜のα型結晶を
β型結晶に変える必要がある。Therefore, it is necessary to change the α-type crystal of the phthalocyanine film formed on the substrate to the β-type crystal for use as an electrophotographic photoreceptor.
【００１０】この点を詳しく述べると、フタロシアニン
の溶液中に基板を浸漬してフタロシアニン膜を付着させ
て成膜する浸漬法では、フタロシアニンの溶液の原料と
して最初からβ型結晶、場合によってはχ型（Ｈ2・Ｐ
ｃ）結晶、或いはε型（Ｃｕ・Ｐｃ）結晶を用いれば、
そのまま基板上にβ型結晶、或いはχ型（Ｈ2・Ｐｃ）
結晶、ε型（Ｃｕ・Ｐｃ）結晶のフタロシアニン膜が成
膜されるが、フタロシアニン原料を蒸発源の抵抗加熱に
より蒸発させて室温の基板上にフタロシアニン膜を蒸着
させる蒸着法の場合は、蒸発源に原料としてフタロシア
ニンのβ型結晶を用いても、基板上に蒸着されたフタロ
シアニン膜はα型結晶になってしまう。そこで基板上に
蒸着し、成膜されたフタロシアニン膜をα型結晶からβ
型結晶に変える方法としては以下の方法が用いられてい
る。To explain this point in detail, in the dipping method in which a substrate is dipped in a solution of phthalocyanine and a phthalocyanine film is attached to form a film, a β-type crystal, or in some cases a χ-type crystal, is used as a raw material of the phthalocyanine solution. (H 2 · P
If c) crystal or ε type (Cu / Pc) crystal is used,
Β type crystal or χ type (H 2 · Pc) directly on the substrate
A crystalline or ε-type (Cu · Pc) crystal phthalocyanine film is formed. In the case of an evaporation method in which a phthalocyanine material is evaporated by resistance heating of an evaporation source and the phthalocyanine film is evaporated on a substrate at room temperature, the evaporation source Even if a β-type crystal of phthalocyanine is used as the raw material, the phthalocyanine film deposited on the substrate becomes an α-type crystal. Therefore, the phthalocyanine film formed by vapor deposition on the substrate was converted from α-type crystals to β
The following method is used as a method for changing to a type crystal.
【００１１】 水素（Ｈ2）、或いはアンモニア（Ｎ
Ｈ3）雰囲気中で３００℃に加熱する。 キシレン（Ｃ6Ｈ4（ＣＨ3）2）、ベンゼン（Ｃ
6Ｈ6）、トルエン（Ｃ6Ｈ5ＣＨ3）等の溶液中に浸漬す
る（場合によっては温度５０〜６０℃に加熱する）。実
際には他の層（例えば電子輸送層）に高分子材料を用い
ることから、の方法が採用されている。Hydrogen (H 2 ) or ammonia (N
H 3 ) Heat to 300 ° C. in an atmosphere. Xylene (C 6 H 4 (CH 3 ) 2), benzene (C
6 H 6 ), toluene (C 6 H 5 CH 3 ) and the like (in some cases, heated to a temperature of 50 to 60 ° C.). In practice, the method is adopted because a polymer material is used for another layer (for example, an electron transport layer).
【００１２】従って、基板上にβ型結晶のフタロシアニ
ン膜を成膜するには、先ず、フタロシアニン膜の原料と
してβ型結晶を用い、これを例えば蒸発源の抵抗加熱に
より蒸発させ、室温の基板上に蒸着させてフタロシアニ
ン膜を成膜する成膜工程の他に、成膜後フタロシアニン
膜の結晶系をα型結晶からβ型結晶に変える工程が必要
となり、成膜工程が煩雑となる問題がある。Therefore, in order to form a β-type crystal phthalocyanine film on a substrate, first, a β-type crystal is used as a raw material for the phthalocyanine film, and this is evaporated by, for example, resistance heating of an evaporation source, and then the substrate is kept at room temperature. In addition to the film-forming process of forming a phthalocyanine film by vapor deposition on the substrate, a process of changing the crystal system of the phthalocyanine film from α-type crystal to β-type crystal after the film formation is required, which causes a problem of complicated film-forming process. .
【００１３】ただ、基板温度を２５０℃に加熱してβ型
結晶のフタロシアニンを蒸着させると、β型結晶のフタ
ロシアニン膜が成膜されるが、基板を所定温度（２５０
℃）に加熱する工程、更には成膜後基板を室温まで冷却
する工程が必要であり、成膜工程に長時間を要するとい
う問題がある。また、基板にアルミニウム（Ａｌ）を用
いると、加熱によって基板のアルミニウムの強度が低下
するという問題も生じる。However, when the substrate temperature is heated to 250 ° C. and β-type crystal phthalocyanine is vapor-deposited, the β-type crystal phthalocyanine film is formed.
Therefore, there is a problem that it takes a long time for the film formation process because a step of heating to (° C.) and a step of cooling the substrate to room temperature after the film formation are required. Further, when aluminum (Al) is used for the substrate, there is a problem that the strength of aluminum of the substrate is lowered by heating.
【００１４】本発明はかかる問題点を解消し、フタロシ
アニン膜の原料結晶系を変えることなく、そのまま基板
上に直接フタロシアニン膜として成膜することが出来る
フタロシアニン膜の成膜方法を提供することを目的とす
る。An object of the present invention is to solve the above problems and provide a method for forming a phthalocyanine film which can be directly formed on a substrate as a phthalocyanine film without changing the raw material crystal system of the phthalocyanine film. And
【００１５】[0015]
【課題を解決するための手段】本発明者らは鋭意検討し
た結果、フタロシアニン膜の原料を急激に加熱、蒸発さ
せることにより、基板上に直接原料の結晶系を維持した
まま蒸着させ、成膜させ得ることを知見した。Means for Solving the Problems As a result of intensive investigations by the present inventors, by rapidly heating and evaporating the raw material of the phthalocyanine film, vapor deposition is performed directly on the substrate while maintaining the crystal system of the raw material. It was found that it can be done.
【００１６】本発明のフタロシアニン膜の成膜方法は前
記知見に基づいてなされたものであり、フタロシアニン
の原料を蒸発させて基板上にフタロシアニン膜を成膜す
る成膜方法において、エレクトロンビーム法によりフタ
ロシアニンの原料を蒸発させて、基板上にフタロシアニ
ン膜を成膜することを特徴とする。The method for forming a phthalocyanine film according to the present invention is based on the above findings. In the method for forming a phthalocyanine film on a substrate by evaporating a phthalocyanine raw material, the phthalocyanine film is formed by an electron beam method. The phthalocyanine film is formed on the substrate by evaporating the raw material.
【００１７】また、前記フタロシアニンの原料はα型結
晶フタロシアニン、β型結晶フタロシアニン、χ型結晶
フタロシアニン、ε型結晶フタロシアニンのいずれか１
種類としてもよい。The raw material of the phthalocyanine is any one of α-type crystal phthalocyanine, β-type crystal phthalocyanine, χ-type crystal phthalocyanine, and ε-type crystal phthalocyanine.
Good as a kind.
【００１８】[0018]
【作用】フタロシアニン膜の原料は加熱により蒸発して
基板上に蒸着し、フタロシアニン膜として成膜される。The raw material of the phthalocyanine film is evaporated by heating and vapor-deposited on the substrate to form a phthalocyanine film.
【００１９】その際、フタロシアニン膜の原料をエレク
トロンビーム法で蒸発させるようにしたので、原料は急
激に加熱され、蒸発するため、フタロシアニンの結晶系
を維持したまま基板上に蒸着する。At this time, since the raw material of the phthalocyanine film is vaporized by the electron beam method, the raw material is rapidly heated and vaporized. Therefore, the phthalocyanine film is vapor-deposited on the substrate while maintaining the crystal system of phthalocyanine.
【００２０】従って、フタロシアニン膜の原料にβ型結
晶を用いれば、基板上に成膜されたフタロシアニン膜の
結晶は従来法のようなα型結晶ではなくβ型結晶とな
る。Therefore, if the β-type crystal is used as the raw material of the phthalocyanine film, the crystal of the phthalocyanine film formed on the substrate becomes a β-type crystal instead of the α-type crystal as in the conventional method.
【００２１】[0021]
【実施例】次に本発明の具体的実施例を比較例と共に説
明する。EXAMPLES Next, specific examples of the present invention will be described together with comparative examples.
【００２２】実施例１ 先ず、真空排気系を備える成膜室内の基板保持装置に縦
50mm、横50mm、厚さ1mmの石英ガラスから成る基板を保
持すると共に、成膜室内の蒸発源内にフタロシアニン膜
の原料としてβ型結晶の銅フタロシアニン（Ｃｕ・Ｐ
ｃ）を充填した。Example 1 First, a substrate holding device in a film forming chamber equipped with a vacuum exhaust system was vertically installed.
A β-type crystal of copper phthalocyanine (Cu · P) is used as a raw material for the phthalocyanine film in the evaporation source in the deposition chamber while holding a substrate made of quartz glass having a thickness of 50 mm, a width of 50 mm and a thickness of 1 mm.
c) was charged.
【００２３】続いて、成膜室内を真空排気系で1.3×10
-3Ｐａ（1×10-5Torr）に設定した後、蒸発源内の原料
にエレクトロンビーム装置（日本真空技術株式会社製、
商品名ＥＧＫ−３型）よりエレクトロンビームを照射し
て原料を加熱、蒸発せしめて基板上に蒸着速度100Å／
秒で蒸着させて膜厚2000Åのフタロシアニン膜を成膜し
た。Then, the film forming chamber is evacuated to 1.3 × 10 5.
After setting -3 Pa (1 x 10 -5 Torr), an electron beam device (manufactured by Nippon Vacuum Technology Co., Ltd.,
Product name EGK-3 type) is irradiated with an electron beam to heat and evaporate the raw material, and the vapor deposition rate is 100Å / on the substrate.
A phthalocyanine film having a film thickness of 2000 Å was formed by vapor deposition in seconds.
【００２４】尚、基板温度は25℃とし、また、エレクト
ロンビーム装置の加速電圧は10kVとした。The substrate temperature was 25 ° C., and the acceleration voltage of the electron beam device was 10 kV.
【００２５】そして基板上に成膜されたフタロシアニン
膜を可視域吸収スペクトル分析し、その結果を図１に曲
線Ａとして示した。The phthalocyanine film formed on the substrate was analyzed by visible absorption spectrum, and the result is shown as curve A in FIG.
【００２６】スペクトル分析の結果、図１の曲線Ａはβ
型結晶のスペクトルである。As a result of the spectrum analysis, the curve A in FIG.
It is a spectrum of a type crystal.
【００２７】比較例１ 先ず、真空排気系を備える成膜室内の基板保持装置に縦
50mm、横50mm、厚さ1mmの石英ガラスから成る基板を保
持すると共に、成膜室内のタングステンフィラメント製
の加熱装置を備えるアルミナルツボから成る蒸発源内に
フタロシアニン膜の原料としてβ型結晶の銅フタロシア
ニン（Ｃｕ・Ｐｃ）を充填した。Comparative Example 1 First, a substrate holding device in a film forming chamber equipped with an evacuation system was vertically installed.
While holding a substrate made of quartz glass of 50 mm, 50 mm in width, and 1 mm in thickness, a β-type copper phthalocyanine ( Cu · Pc) was filled.
【００２８】続いて、成膜室内を真空排気系で1.3×10
-3Ｐａ（1×10-5Torr）に設定した後、蒸発源内の原料
を蒸発源の抵抗加熱で加熱、蒸発せしめて基板上に蒸着
速度10Å／分で蒸着させて膜厚2000Åのフタロシアニン
膜を成膜した。Then, the film forming chamber is evacuated to 1.3 × 10 5.
After setting to -3 Pa (1 x 10 -5 Torr), the raw material in the evaporation source is heated and evaporated by resistance heating of the evaporation source and evaporated on the substrate at an evaporation rate of 10 Å / min to form a 2000 Å-thick phthalocyanine film. Was deposited.
【００２９】尚、基板温度は25℃とし、また、蒸発源温
度は420℃とした。The substrate temperature was 25 ° C., and the evaporation source temperature was 420 ° C.
【００３０】そして基板上に成膜されたフタロシアニン
膜を可視域吸収スペクトル分析し、その結果を図１に曲
線Ｂとして示した。The phthalocyanine film formed on the substrate was subjected to visible absorption spectrum analysis, and the result is shown as curve B in FIG.
【００３１】スペクトル分析の結果、図１の曲線Ｂはα
型結晶のスペクトルである。As a result of the spectrum analysis, the curve B in FIG.
It is a spectrum of a type crystal.
【００３２】図１から明らかなように、本発明方法では
フタロシアニン膜の結晶を原料の結晶、即ちβ型結晶を
変えることなく成膜出来た。As is apparent from FIG. 1, according to the method of the present invention, the crystal of the phthalocyanine film can be formed without changing the raw material crystal, that is, the β-type crystal.
【００３３】これに対し、比較例１の場合は、フタロシ
アニンの原料はβ型結晶であったにもかかわらず、成膜
後のフタロシアニン膜はα型結晶に変わっていた。On the other hand, in Comparative Example 1, although the phthalocyanine raw material was β-type crystal, the phthalocyanine film after film formation was changed to α-type crystal.
【００３４】従って、本発明方法では基板上に直接フタ
ロシアニン膜の原料の結晶系を変えることなく、フタロ
シアニン膜を成膜出来ることが確認された。Therefore, it was confirmed that the phthalocyanine film can be formed directly on the substrate by the method of the present invention without changing the crystal system of the raw material of the phthalocyanine film.
【００３５】実施例２ 基板として縦50mm、横50mm、厚さ1mmのアルミニウムを
用いた以外は前記実施例１と同様の方法で、基板上に膜
厚2000Åのフタロシアニン膜を成膜した。Example 2 A phthalocyanine film having a thickness of 2000 Å was formed on a substrate in the same manner as in Example 1 except that aluminum having a length of 50 mm, a width of 50 mm and a thickness of 1 mm was used as the substrate.
【００３６】そして基板上に成膜されたフタロシアニン
膜を可視域吸収スペクトル分析したところ、フタロンシ
アニン膜はβ型結晶であることが分かった。When the phthalocyanine film formed on the substrate was analyzed by visible absorption spectrum, it was found that the phthalone cyanine film was β-type crystal.
【００３７】比較例２ 基板として縦50mm、横50mm、厚さ1mmのアルミニウムを
用いた以外は前記比較例１と同様の方法で、基板上に膜
厚2000Åのフタロシアニン膜を成膜した。Comparative Example 2 A phthalocyanine film having a film thickness of 2000 Å was formed on a substrate in the same manner as in Comparative Example 1 except that aluminum having a length of 50 mm, a width of 50 mm and a thickness of 1 mm was used as the substrate.
【００３８】そして基板上に成膜されたフタロシアニン
膜を可視域吸収スペクトル分析したところ、フタロンシ
アニン膜はα型結晶であることが分かった。When the phthalocyanine film formed on the substrate was analyzed by visible absorption spectrum, it was found that the phthalone cyanine film was an α-type crystal.
【００３９】実施例３ フタロシアニン膜の原料としてα型結晶の銅フタロシア
ニン（Ｃｕ・Ｐｃ）を用いた以外は前記実施例１と同様
の方法で基板上に膜厚2000Åのフタロシアニン膜を成膜
した。Example 3 A phthalocyanine film having a thickness of 2000 Å was formed on a substrate by the same method as in Example 1 except that α-type crystal copper phthalocyanine (Cu.Pc) was used as a raw material for the phthalocyanine film.
【００４０】そして基板上に成膜されたフタロシアニン
膜を可視域吸収スペクトル分析したところ、フタロンシ
アニン膜はα型結晶であることが分かった。When the phthalocyanine film formed on the substrate was analyzed by visible absorption spectrum, it was found that the phthalone cyanine film was an α-type crystal.
【００４１】比較例３ フタロシアニン膜の原料としてα型結晶の銅フタロシア
ニン（Ｃｕ・Ｐｃ）を用いた以外は前記比較例１と同様
の方法で基板上に膜厚2000Åのフタロシアニン膜を成膜
した。Comparative Example 3 A phthalocyanine film having a thickness of 2000 Å was formed on a substrate in the same manner as in Comparative Example 1 except that α-type crystal copper phthalocyanine (Cu.Pc) was used as a raw material for the phthalocyanine film.
【００４２】そして基板上に成膜されたフタロシアニン
膜を可視域吸収スペクトル分析したところ、フタロンシ
アニン膜はα型結晶であることが分かった。When the phthalocyanine film formed on the substrate was analyzed by visible absorption spectrum, it was found that the phthalone cyanine film was an α-type crystal.
【００４３】実施例４ フタロシアニン膜の原料としてχ型結晶の無金属フタロ
シアニン（Ｈ2・Ｐｃ）を用いた以外は前記実施例１と
同様の方法で基板上に膜厚2000Åのフタロシアニン膜を
成膜した。Example 4 A phthalocyanine film having a thickness of 2000 Å was formed on a substrate in the same manner as in Example 1 except that χ-type metal-free phthalocyanine (H 2 · Pc) was used as a raw material for the phthalocyanine film. did.
【００４４】そして基板上に成膜されたフタロシアニン
膜を可視域吸収スペクトル分析したところ、フタロンシ
アニン膜はχ型結晶であることが分かった。When the phthalocyanine film formed on the substrate was analyzed by visible absorption spectrum, it was found that the phthalone cyanine film was a χ type crystal.
【００４５】比較例４ フタロシアニン膜の原料としてχ型結晶の無金属フタロ
シアニン（Ｈ2・Ｐｃ）を用いた以外は前記比較例１と
同様の方法で基板上に膜厚2000Åのフタロシアニン膜を
成膜した。Comparative Example 4 A phthalocyanine film having a film thickness of 2000 Å was formed on a substrate in the same manner as in Comparative Example 1 except that χ-type metal-free phthalocyanine (H 2 .Pc) was used as a raw material for the phthalocyanine film. did.
【００４６】そして基板上に成膜されたフタロシアニン
膜を可視域吸収スペクトル分析したところ、フタロンシ
アニン膜はα型結晶であることが分かった。When the phthalocyanine film formed on the substrate was analyzed by visible absorption spectrum, it was found that the phthalone cyanine film was an α-type crystal.
【００４７】実施例５ フタロシアニン膜の原料としてε型結晶の銅フタロシア
ニン（Ｃｕ・Ｐｃ）を用いた以外は前記実施例１と同様
の方法で基板上に膜厚2000Åのフタロシアニン膜を成膜
した。Example 5 A phthalocyanine film having a thickness of 2000 Å was formed on a substrate in the same manner as in Example 1 except that ε-type copper phthalocyanine (Cu.Pc) was used as a raw material for the phthalocyanine film.
【００４８】そして基板上に成膜されたフタロシアニン
膜を可視域吸収スペクトル分析したところ、フタロンシ
アニン膜はε型結晶であることが分かった。When the phthalocyanine film formed on the substrate was analyzed by visible absorption spectrum, it was found that the phthalone cyanine film was an ε-type crystal.
【００４９】比較例５ フタロシアニン膜の原料としてε型結晶の銅フタロシア
ニン（Ｃｕ・Ｐｃ）を用いた以外は前記比較例１と同様
の方法で基板上に膜厚2000Åのフタロシアニン膜を成膜
した。Comparative Example 5 A phthalocyanine film having a thickness of 2000 Å was formed on a substrate by the same method as in Comparative Example 1 except that ε-type crystal copper phthalocyanine (Cu.Pc) was used as a raw material for the phthalocyanine film.
【００５０】そして基板上に成膜されたフタロシアニン
膜を可視域吸収スペクトル分析したところ、フタロンシ
アニン膜はα型結晶であることが分かった。When the phthalocyanine film formed on the substrate was analyzed by visible absorption spectrum, it was found that the phthalone cyanine film was an α-type crystal.
【００５１】本発明方法では、フタロシアニン膜の原料
がエレクトロンビームにより急激に加熱されるため、蒸
発時に分子状態となる前に蒸発する、即ち、フタロシア
ニン膜の原料の結晶系を保ったまま蒸発するためと考え
られる。In the method of the present invention, since the raw material of the phthalocyanine film is rapidly heated by the electron beam, it evaporates before becoming a molecular state at the time of vaporization, that is, it vaporizes while maintaining the crystal system of the raw material of the phthalocyanine film. it is conceivable that.
【００５２】これに対し、比較例（１，２，３，４，
５）の場合は、フタロシアニン膜の原料としてα型結
晶、β型結晶、χ型結晶、ε型結晶を用いても、成膜さ
れたフタロシアニン膜の結晶はいずれもα型結晶にしか
ならなかった。これは基板が室温なため、基板上に蒸着
したフタロシアニンがより不安定なα型結晶にしかなれ
ないことを意味する。即ち、蒸発源で抵抗加熱された原
料のフタロシアニンは徐々に加熱されることにより分子
状態となり、蒸発時にフタロシアニン膜の原料の結晶系
が失われるためと考えられる。On the other hand, comparative examples (1, 2, 3, 4,
In the case of 5), even if α-type crystals, β-type crystals, χ-type crystals, and ε-type crystals were used as the raw materials of the phthalocyanine film, the formed phthalocyanine film crystals were all α-type crystals. . This means that since the substrate is at room temperature, the phthalocyanine vapor-deposited on the substrate can only be a more unstable α-type crystal. That is, it is considered that the raw material phthalocyanine, which is resistance-heated by the evaporation source, is gradually heated to be in a molecular state, and the crystal system of the raw material of the phthalocyanine film is lost during evaporation.
【００５３】実施例６ 基板温度を50℃とした以外は前記実施例１と同様の方法
で基板上に膜厚2000Åのフタロシアニン膜を成膜した。Example 6 A phthalocyanine film having a thickness of 2000 Å was formed on a substrate by the same method as in Example 1 except that the substrate temperature was 50 ° C.
【００５４】尚、基板の昇温速度は5℃／分間とし、ま
た、基板の降温速度は5℃／分間とした。The substrate heating rate was 5 ° C./minute, and the substrate cooling rate was 5 ° C./minute.
【００５５】そして基板上に成膜されたフタロシアニン
膜を可視域吸収スペクトル分析したところ、フタロンシ
アニン膜はβ型結晶であることが分かった。When the phthalocyanine film formed on the substrate was analyzed by visible absorption spectrum, it was found that the phthalone cyanine film was β-type crystal.
【００５６】比較例６ 基板温度を50℃とした以外は前記比較例１と同様の方法
で基板上に膜厚2000Åのフタロシアニン膜を成膜した。Comparative Example 6 A phthalocyanine film having a film thickness of 2000 Å was formed on a substrate by the same method as in Comparative Example 1 except that the substrate temperature was 50 ° C.
【００５７】尚、基板の昇温速度は5℃／分間とし、ま
た、基板の降温速度は5℃／分間とした。The substrate heating rate was 5 ° C./minute, and the substrate cooling rate was 5 ° C./minute.
【００５８】そして基板上に成膜されたフタロシアニン
膜を可視域吸収スペクトル分析したところ、フタロンシ
アニン膜はα型結晶であることが分かった。When the phthalocyanine film formed on the substrate was analyzed by visible absorption spectrum, it was found that the phthalone cyanine film was an α-type crystal.
【００５９】実施例７ 基板温度を100℃とした以外は前記実施例１と同様の方
法で基板上に膜厚2000Åのフタロシアニン膜を成膜し
た。Example 7 A phthalocyanine film having a film thickness of 2000 Å was formed on a substrate by the same method as in Example 1 except that the substrate temperature was 100 ° C.
【００６０】尚、基板の昇温速度は5℃／分間とし、ま
た、基板の降温速度は5℃／分間とした。The substrate heating rate was 5 ° C./minute, and the substrate cooling rate was 5 ° C./minute.
【００６１】そして基板上に成膜されたフタロシアニン
膜を可視域吸収スペクトル分析したところ、フタロンシ
アニン膜はβ型結晶であることが分かった。When the phthalocyanine film formed on the substrate was analyzed by visible absorption spectrum, it was found that the phthalone cyanine film was β-type crystal.
【００６２】比較例７ 基板温度を100℃とした以外は前記比較例１と同様の方
法で基板上に膜厚2000Åのフタロシアニン膜を成膜し
た。Comparative Example 7 A phthalocyanine film having a film thickness of 2000 Å was formed on a substrate by the same method as in Comparative Example 1 except that the substrate temperature was 100 ° C.
【００６３】尚、基板の昇温速度は5℃／分間とし、ま
た、基板の降温速度は5℃／分間とした。The substrate heating rate was 5 ° C./minute, and the substrate cooling rate was 5 ° C./minute.
【００６４】そして基板上に成膜されたフタロシアニン
膜を可視域吸収スペクトル分析したところ、フタロンシ
アニン膜はα型結晶であることが分かった。When the phthalocyanine film formed on the substrate was analyzed by visible absorption spectrum, it was found that the phthalone cyanine film was an α-type crystal.
【００６５】比較例８ 基板として縦50mm、横50mm、厚さ1mmのアルミニウムを
用い、基板温度を250℃とした以外は前記比較例１と同
様の方法で基板上に膜厚2000Åのフタロシアニン膜を成
膜した。Comparative Example 8 A phthalocyanine film having a thickness of 2000 Å was formed on a substrate in the same manner as in Comparative Example 1 except that aluminum having a length of 50 mm, a width of 50 mm and a thickness of 1 mm was used as the substrate and the substrate temperature was 250 ° C. A film was formed.
【００６６】尚、基板の昇温速度は5℃／分間とし、ま
た、基板の降温速度は5℃／分間とした。The substrate heating rate was 5 ° C./minute, and the substrate cooling rate was 5 ° C./minute.
【００６７】そして基板上に成膜されたフタロシアニン
膜を可視域吸収スペクトル分析したところ、フタロンシ
アニン膜はβ型結晶であることが分かった。When the phthalocyanine film formed on the substrate was analyzed by visible absorption spectrum, it was found that the phthalone cyanine film was β-type crystal.
【００６８】比較例８のように基板温度を250℃以上に
することにより、成膜されたフタロシアニン膜の結晶系
をβ型結晶系とすることが出来るが、基板の加熱処理、
成膜後基板を室温まで冷却させる必要があるため、生産
性が低い。By setting the substrate temperature to 250 ° C. or higher as in Comparative Example 8, the crystal system of the formed phthalocyanine film can be changed to the β-type crystal system.
Since it is necessary to cool the substrate to room temperature after film formation, productivity is low.
【００６９】前述のように、本発明方法では原料の結晶
系を維持することが出来るので、用いる原料がβ型結晶
であれば基板上に蒸着し成膜されたフタロシアニン膜は
β型結晶となり、α型結晶であればフタロシアニン膜は
α型結晶と成る。同様に用いる原料がχ型（Ｈ2・Ｐ
ｃ）結晶であれば基板上に蒸着し成膜されたフタロシア
ニン膜はχ型結晶となり、ε型（Ｃｕ・Ｐｃ）結晶であ
ればフタロシアニン膜はε型結晶と成る。本発明方法は
フタロシアニン膜の原料の結晶系を変えることなく、基
板上に直接フタロシアニン膜を成膜出来ることが最大の
特徴である。As described above, since the crystal system of the raw material can be maintained in the method of the present invention, if the raw material used is β type crystal, the phthalocyanine film deposited and formed on the substrate becomes β type crystal, If it is an α type crystal, the phthalocyanine film becomes an α type crystal. The raw material used in the same manner is χ type (H 2 · P
In the case of c) crystal, the phthalocyanine film formed by vapor deposition on the substrate is a χ type crystal, and in the case of ε type (Cu · Pc) crystal, the phthalocyanine film is an ε type crystal. The most characteristic feature of the method of the present invention is that the phthalocyanine film can be directly formed on the substrate without changing the crystal system of the raw material of the phthalocyanine film.
【００７０】前記本発明実施例ではフタロシアニンを蒸
着させる際の基板温度を25℃（室温）、50℃、100℃と
したが、本発明はこれに限定されるものではない。In the embodiments of the present invention, the substrate temperature for vapor deposition of phthalocyanine was 25 ° C. (room temperature), 50 ° C. and 100 ° C., but the present invention is not limited to this.
【００７１】また、前記本発明実施例ではフタロシアニ
ン膜の原料をエレクトロンビームで加熱、蒸発させ、基
板上に蒸着、成膜するようにしたが、フタロシアニン膜
の原料に急激な加熱を与えて蒸発させ、基板上に蒸着、
成膜することが出来る蒸着法置であればよく、前記エレ
クトロンビームによる蒸着法の他に、フラッシュ蒸着
法、レーザー蒸着法が挙げられるが、これらフラッシュ
蒸着法、レーザー蒸着法によるフタロシアニン膜の成膜
方法はいまだに確立しておらず、今後の研究課題であ
る。In the embodiment of the present invention, the raw material of the phthalocyanine film is heated and evaporated by the electron beam to deposit and form the film on the substrate. However, the raw material of the phthalocyanine film is rapidly heated and evaporated. , Vapor deposition on the substrate,
Any vapor deposition method capable of forming a film may be used, and examples of the vapor deposition method using the electron beam include flash vapor deposition method and laser vapor deposition method. These flash vapor deposition method and laser vapor deposition method are used to form a phthalocyanine film. The method has not been established yet and is a subject for future research.
【００７２】[0072]
【発明の効果】本発明によるときは、フタロシアニン膜
の原料をエレクトロンビーム法により加熱し、蒸発させ
て基板上にフタロシアニン膜を成膜するようにしたの
で、従来法のように基板上への成膜後にフタロシアニン
膜の結晶系を変える工程を必要としないため、基板上に
直接原料の結晶系と同じ結晶系のフタロシアニン膜を極
めて容易に成膜することが出来るという効果がある。According to the present invention, the raw material of the phthalocyanine film is heated by the electron beam method and evaporated to form the phthalocyanine film on the substrate. Since the step of changing the crystal system of the phthalocyanine film after the film is not required, there is an effect that a phthalocyanine film of the same crystal system as the raw material crystal system can be extremely easily formed directly on the substrate.
【図１】 本発明実施例並びに比較例により成膜された
フタロシアニン膜の吸光度と波長との関係を示す特性線
図、FIG. 1 is a characteristic diagram showing the relationship between the absorbance and the wavelength of a phthalocyanine film formed by Examples of the present invention and Comparative Examples,
【図２】 主な電子写真感光体の構成を示す説明截断面
図。FIG. 2 is an explanatory sectional view showing the configuration of a main electrophotographic photosensitive member.
フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｇ０３Ｇ 5/06 ３７１ Continuation of front page (51) Int.Cl. 6 Identification number Office reference number FI technical display location G03G 5/06 371
Claims (2)
上にフタロシアニン膜を成膜する成膜方法において、エ
レクトロンビーム法によりフタロシアニンの原料を蒸発
させて、基板上にフタロシアニン膜を成膜することを特
徴とするフタロシアニン膜の成膜方法。1. A method for forming a phthalocyanine film on a substrate by evaporating a phthalocyanine material, wherein the phthalocyanine material is evaporated by an electron beam method to form a phthalocyanine film on the substrate. And a method for forming a phthalocyanine film.
タロシアニン、β型結晶フタロシアニン、χ型結晶フタ
ロシアニン、ε型結晶フタロシアニンのいずれか１種類
であることを特徴とする請求項第１項に記載のフタロシ
アニン膜の成膜方法。2. The phthalocyanine according to claim 1, wherein the raw material of the phthalocyanine is any one of α-type crystal phthalocyanine, β-type crystal phthalocyanine, χ-type crystal phthalocyanine, and ε-type crystal phthalocyanine. Method of forming a film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6001772A JPH07211958A (en) | 1994-01-12 | 1994-01-12 | Formation of phthalocyanine film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6001772A JPH07211958A (en) | 1994-01-12 | 1994-01-12 | Formation of phthalocyanine film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07211958A true JPH07211958A (en) | 1995-08-11 |
Family
ID=11510873
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6001772A Pending JPH07211958A (en) | 1994-01-12 | 1994-01-12 | Formation of phthalocyanine film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07211958A (en) |
-
1994
- 1994-01-12 JP JP6001772A patent/JPH07211958A/en active Pending
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