JPS63308036A - Plasma-polymerized thin film from quinacridone - Google Patents
Plasma-polymerized thin film from quinacridoneInfo
- Publication number
- JPS63308036A JPS63308036A JP4500887A JP4500887A JPS63308036A JP S63308036 A JPS63308036 A JP S63308036A JP 4500887 A JP4500887 A JP 4500887A JP 4500887 A JP4500887 A JP 4500887A JP S63308036 A JPS63308036 A JP S63308036A
- Authority
- JP
- Japan
- Prior art keywords
- quinacridone
- plasma
- thin film
- film
- polymerized
- 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
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000010409 thin film Substances 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000010521 absorption reaction Methods 0.000 claims abstract description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 3
- 239000010937 tungsten Substances 0.000 claims abstract description 3
- 230000009102 absorption Effects 0.000 claims abstract 2
- 230000003595 spectral effect Effects 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 38
- 238000006116 polymerization reaction Methods 0.000 abstract description 8
- 239000011521 glass Substances 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 239000000654 additive Substances 0.000 abstract description 2
- 238000002265 electronic spectrum Methods 0.000 abstract description 2
- 238000000859 sublimation Methods 0.000 abstract description 2
- 230000008022 sublimation Effects 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001197 polyacetylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002952 polymeric resin Substances 0.000 description 2
- 239000001054 red pigment Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- -1 For example Substances 0.000 description 1
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- QQGNLKJAIVSNCO-UHFFFAOYSA-N N-butylformamide Chemical compound CCCCNC=O QQGNLKJAIVSNCO-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 210000004905 finger nail Anatomy 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 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 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は溶剤不溶でかつ光電変換能を有するキナクリド
ンのプラズマ重合Ｒ＠に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to plasma polymerization R@ of quinacridone which is insoluble in solvents and has photoelectric conversion ability.
（従来の技術）
光堪変換素子即ち大局電池は、結晶シリコン或いは非品
性のシリコンで作られる無機系が殆んどである。近年、
フタロシアニンやメロシアニン等の色素或いは特定の物
質をドーピングしたポリアセチレン等を利用した有機系
の太陽電池も研究されている。有機系の特徴は、安価で
可とう性良好であり、大面積のフィルム状である点であ
る。(Prior Art) Photovoltaic conversion elements, ie, global batteries, are mostly inorganic ones made of crystalline silicon or non-quality silicon. recent years,
Organic solar cells using polyacetylene doped with dyes such as phthalocyanine or merocyanine or specific substances are also being researched. The characteristics of organic materials are that they are inexpensive, have good flexibility, and are in the form of a large-area film.
一方、有機系太陽電池においては、有機系半導体の力学
物性の向上、太陽光の吸収効果の増大、キャリアー発生
効率の向上、内部抵抗の低下及び長期使用に耐える安定
性等が必要であるが、未だ満足なものはない。On the other hand, in organic solar cells, it is necessary to improve the mechanical properties of organic semiconductors, increase the sunlight absorption effect, improve carrier generation efficiency, lower internal resistance, and stability that can withstand long-term use. Nothing is satisfying yet.
しかしこれらの色素類、或いはポリアセチレン等の有機
導電材料は、そのままでは高分子化や薄膜化できず、例
えば高分子量化する為には、重合性を有する官能基を導
入したり、電解重合という特殊な方法により高分子化或
いは薄膜化したり（特開昭６０−２８２７８号公報）、
或いは他の高分子樹脂の中に分散して使うしかなかった
。これらの方法では、分子構造の修飾の困」さや修飾に
よる性能の低下、重合膜の力学的性質や化学的安定性に
劣る、或いは重合の困難さがあった。他の高分子樹脂中
へ分散して使用する方法では、希釈による性能低下、分
散ムラ及び成膜性の低下がある為に、良好な光電変換素
子は得られていない。However, these dyes or organic conductive materials such as polyacetylene cannot be made into polymers or thin films as they are. For example, in order to increase the molecular weight, it is necessary to introduce polymerizable functional groups or use special electrolytic polymerization. Polymerized or thinned by a method (Japanese Unexamined Patent Publication No. 60-28278),
Alternatively, it had no choice but to be used by dispersing it in other polymer resins. These methods have problems in modifying the molecular structure, deterioration of performance due to modification, poor mechanical properties and chemical stability of the polymerized film, or difficulty in polymerization. In the method of dispersing it in other polymeric resins, a good photoelectric conversion element cannot be obtained because there is a decrease in performance due to dilution, uneven dispersion, and a decrease in film-forming properties.
（発明が解決しようとする問題点）
本発明の目的は化学的、物理的に安定で光電変換機能を
有する薄膜状のキナクリドン重合膜を提供するにあり、
他の目的は工業的容易かつ安価な製造方法を提供するに
ある。(Problems to be Solved by the Invention) An object of the present invention is to provide a thin quinacridone polymer film that is chemically and physically stable and has a photoelectric conversion function.
Another object is to provide an industrially easy and inexpensive manufacturing method.
（問題点を解決する為の手段）
本発明は、溶剤不溶でかつ光電変換能を有するキナクリ
ドンのプラズマ重合薄膜である。(Means for Solving the Problems) The present invention is a plasma-polymerized thin film of quinacridone that is insoluble in solvents and has photoelectric conversion ability.
本発明に使用するキナクリドンは一般的に赤色顔料とし
て知られているものであり、例えば０、１． Ｐｉｇｍ
ｅｎｔ Ｒｅｄ １２２． Ｃ，１，Ｐｉｇｍｅｎ
ｔＶｉｏｌｅｔ １９として知られている。これらの
キナクリドンは下記一般式で示され、α−２β−９γ−
の結晶系を有する。キナクリドンの誘導体として、ベン
ゼン環の水素原子の少なくとも１つが塩素、臭素等のハ
ロゲンに置換したものも使用可能である。The quinacridone used in the present invention is generally known as a red pigment, for example, 0, 1. Pigm
ent Red 122. C,1,Pigmen
It is known as tViolet 19. These quinacridones are represented by the following general formula, α-2β-9γ-
It has a crystal system of As derivatives of quinacridone, those in which at least one hydrogen atom of the benzene ring is substituted with a halogen such as chlorine or bromine can also be used.
キナクリドンのモノマー及び通常の方法による蒸着膜の
ＩＲ％ＵＶ−ｖｘｓｙｔ子スペクトルは同一のスペクト
ルを示す。プラズマ重合膜のＩＲスペクトルではモノマ
ーの主要な吸収ピーク（１６２５ｃｍ 、１５８３ｃ
ｍ 、１４７０ｃｍ 。The IR% UV-vxsyt spectra of the quinacridone monomer and the film deposited by the conventional method show the same spectra. The IR spectrum of the plasma polymerized film shows the main absorption peaks of the monomer (1625 cm, 1583 cm
m, 1470 cm.
１８４８ ｃｍ−’ 、 ７６７ ａｍ−’ ）は
残存するが、全体的に平坦となる。ＵＶ−ＶＩＳｇ子ス
ペクトルでは、モノマーの２つの吸収ピーク（５２４ｎ
ｍ。1848 cm-', 767 am-') remain, but are generally flat. In the UV-VIS particle spectrum, two absorption peaks of the monomer (524n
m.
５６２ｎｍ）がいずれも低波長側ヘシフトしており、薄
膜化する事によりいく分モノマー分子の共役系が短かく
なった事が示される。従って外観も七ツマ−や蒸着膜で
は赤或いは紫色を呈するが。562 nm) are all shifted to the lower wavelength side, indicating that the conjugated system of the monomer molecules has become somewhat shorter due to the thinner film. Therefore, the appearance also appears red or purple in the case of a seven-pointed or vapor-deposited film.
本発明のプラズマ重合膜ではやや黄味を帯びた膜が得ら
れる。The plasma polymerized membrane of the present invention provides a slightly yellowish membrane.
頃の形ｆ譜、構造についてはモノマーや蒸着膜が結晶構
造による大きな粒子や島構造を有した不均一な膜しか形
成できないのに対して、プラズマ重合膜では肉眼、光学
頗微鑓のレベルではもちろん、電子＠微鏡のレベルでも
均一で比較的平滑な膜であり、両者の違いは明確に区別
できる。In terms of shape and structure, monomer and vapor-deposited films can only form non-uniform films with large particles and island structures due to crystal structures, whereas plasma polymerized films can only be formed at the level of the naked eye and optical scale. Of course, even at the electron microscopic level, the film is uniform and relatively smooth, and the difference between the two can be clearly distinguished.
膜の厚さはプラズマ重合条件により任意に設定できるが
％通常０．０１〜５μｍ１好ましくは０．０５〜１μｍ
１更に好ましくは０．１〜０．５μｍである。The thickness of the film can be arbitrarily set depending on the plasma polymerization conditions, but it is usually 0.01 to 5 μm, preferably 0.05 to 1 μm.
1, more preferably 0.1 to 0.5 μm.
膜厚が０．０１μｍより薄ければ、膜の強度や光電変換
能は十分ではないし、一方５μｍより厚い場合は膜の不
均一性やヒビ割れが生じ、かつ光電変換能も十分でない
。If the film thickness is less than 0.01 μm, the strength and photoelectric conversion ability of the film will not be sufficient, while if it is thicker than 5 μm, non-uniformity and cracking will occur in the film, and the photoelectric conversion ability will not be sufficient.
キナクリドンのプラズマ重合膜はモノマーの少なくとも
一部が他のモノマーと結合している為に、非結晶性の平
滑で硬くかつ溶剤不溶性の膜となると推測される。ここ
で溶剤とは、七ツマ−の溶剤はもちろん一般的な溶剤、
例えばアセトン、メチルエチルケトン、キシレン、トル
エン、クロロホルム、１−クロロナフタレン、 ｔ−
ブチルホルムアミド等をいう。Since at least a portion of the monomers in the plasma-polymerized film of quinacridone are bonded to other monomers, it is assumed that the film is amorphous, smooth, hard, and insoluble in solvents. Solvent here refers to not only ordinary solvents but also general solvents,
For example, acetone, methyl ethyl ketone, xylene, toluene, chloroform, 1-chloronaphthalene, t-
Refers to butylformamide, etc.
本発明のプラズマ重合膜も、モノマー及びその蒸着膜と
同様に光電変換能を有する。光電変換能の変換効率（η
（３））は、例えば透明でかつ導に性を有するＩＴＯガ
ラス上にキナクリドンプラズマ重合膜を形成させ、つい
でプラズマ重合膜上にアルミニウムを蒸着させてＭＩａ
型セルをつくり、ＩＴＯとアルミニウムを両極として、
アルミニウム側よりタングステン光を照射し両Ｗｉ価に
かかる電圧（Ｖｏｃ ：開放端電圧）及び回路を形成し
た時の電流（Ｊｓｃ ：短絡電流）及びＴｏｅ−ｖｃｃ
の形状（ｆｆ：フィルファクター）より算出される
。The plasma polymerized film of the present invention also has photoelectric conversion ability like the monomer and its vapor-deposited film. Conversion efficiency of photoelectric conversion capacity (η
(3)) For example, a quinacridone plasma-polymerized film is formed on transparent and conductive ITO glass, and then aluminum is vapor-deposited on the plasma-polymerized film to create MIa.
Make a type cell and use ITO and aluminum as both poles.
Voltage applied to both Wi values (Voc: open end voltage), current when a circuit is formed (Jsc: short circuit current) and Toe-vcc when tungsten light is irradiated from the aluminum side
It is calculated from the shape (ff: fill factor).
本発明のキナクリドンプラズマ重合＃膜を用いたセルで
は、Ｊｓｃは通常１ｎＡ／Ｃｍ以上、好ましくはｌ Ｑ
ｎＡ／Ｃｍ以上、更に好ましくは１００ｎｌ／Ｃｍ以
上であり、これらの値は通常の蒸着膜の１０００ ｎＡ
／ｃｍには及ばない。これは、プラズマ重合膜と蒸着膜
におけるモノマー構造の維持性（高分子化度）及び分子
の配列（スクッキング）状態によるものである。又ＶＯ
Ｃは通常０，１７以上、好ましくは０．２ｖ以上、更に
好ましくは０．５ｖ以上であり、光電変換能の変換効率
η（埒は通常１×１０ ％以上、好ましくは１×１０
％以上、更に好ましくはＩＸＩ Ｏ％以上である。In a cell using the quinacridone plasma polymerized film of the present invention, Jsc is usually 1 nA/Cm or more, preferably l Q
nA/Cm or more, more preferably 100 nl/Cm or more, and these values are higher than 1000 nA of a normal vapor deposited film.
/cm. This is due to the maintainability of the monomer structure (degree of polymerization) and molecular arrangement (scooking) state in the plasma polymerized film and the vapor deposited film. Also VO
C is usually 0.17 or more, preferably 0.2V or more, more preferably 0.5V or more, and the conversion efficiency η of photoelectric conversion ability is usually 1 x 10% or more, preferably 1 x 10
% or more, more preferably IXIO% or more.
次に、本発明のプラズマ重合膜の製法の一例を示して具
体的に説明する。Next, an example of the method for manufacturing the plasma polymerized membrane of the present invention will be specifically explained.
プラズマ反応器は、第１図に示すような平行平板の内部
電極を有するペルジャー型の反応器である。ＩＴＯガラ
スを上部電極上にはりつけ、反応器内部を十分アルゴン
ガスで置換機内圧を１０−８〜ｌＯ°ｔｏｒｒに保ち、
平行平板電極に高周波を印加し低温プラズマを発生させ
る。ついで下部電極の上方においたモノマー容器を加熱
し一定時間キナクリドンを加熱昇華させる。加熱昇華し
たキナクリドンは、ＩＴＯガラス板上にプラズマ重合薄
膜として形成される。重合薄膜の膜厚は、プラズマ条件
及びキナクリドンの昇華条件（速度１時間）により調整
できる。プラズマの出力は通常数Ｗ〜２００Ｗ、好まし
くは２〜ｉｏｏｗであり、重合時間も数分以下で十分で
ある。The plasma reactor is a Pelger type reactor having parallel plate internal electrodes as shown in FIG. Attach ITO glass to the upper electrode, replace the inside of the reactor with sufficient argon gas, and maintain the internal pressure at 10-8 to 10° torr.
High-frequency waves are applied to parallel plate electrodes to generate low-temperature plasma. Next, the monomer container placed above the lower electrode is heated to sublimate the quinacridone for a certain period of time. The heat-sublimated quinacridone is formed as a plasma-polymerized thin film on an ITO glass plate. The thickness of the polymerized thin film can be adjusted by plasma conditions and quinacridone sublimation conditions (rate: 1 hour). The output of the plasma is usually several W to 200 W, preferably 2 to ioow, and a polymerization time of several minutes or less is sufficient.
（本発明の効果）
本発明は、化学的に、又物理的に安定でかつ光電変換能
を有するキナクリドンプラズマ重合膜を他の副材料や添
加物等を用いる事なく、又原料への重合可能な官能基の
導入や微粒子化或いは他のポリマーへの混合といった復
雑でコストのかかる工程も必要とせず、更に均一で平滑
な薄膜が得られるという点で、工業的に極めて有利であ
る。(Effects of the present invention) The present invention makes it possible to polymerize a quinacridone plasma polymerized film, which is chemically and physically stable and has photoelectric conversion ability, into a raw material without using other auxiliary materials or additives. It is industrially extremely advantageous in that it does not require complicated and costly steps such as introduction of functional groups, microparticle formation, or mixing with other polymers, and can provide a uniform and smooth thin film.
本発明のキナクリドンプラズマ重合膜は赤色簿膜、コー
テイング膜としてのみでなく、導電性材料や充電変換素
子として使用可能である。The quinacridone plasma polymerized film of the present invention can be used not only as a red book film or a coating film, but also as a conductive material or a charge conversion element.
（実施例） 以下、実施例を示して本発明を更に詳細に説明する。(Example) Hereinafter, the present invention will be explained in more detail by showing examples.
実施例
赤色顔料のキナクリドン（γ型）１ｏｍｇ をＫＢｒ錠
剤成型機にて成型したディスクをペルジャー型反応器内
に設置した加熱用ヒーター上にのせる。高電導度ＩＴＯ
ガラス板を１０ｃｍ径の平行平板電極の上部電極に張り
付ける。ペルジャー内を１０ｔｏｒｒ 以下に脱気し
アルゴンを導入する操作を８回繰り返した後、ペルジャ
ー内の圧力をアルゴンで０．１ｔｏｒｒに設定し％１８
．５６ＭＪ（ｚの高周波を第１表に示すプラズマ出力に
て印加してアルゴンプラズマを発生させ、次いで加熱用
ヒーターを加熱しキナクリドンを昇華させた。モノマー
供給シャッターにより５秒間キナクリドンモノマーをプ
ラズマ中へ供給し、ＩＴＯガラス上へキナクリドンのプ
ラズマ重合膜を形成させた。EXAMPLE A disk containing 1 omg of red pigment quinacridone (γ type) molded using a KBr tablet molding machine was placed on a heating heater installed in a Pelger type reactor. High conductivity ITO
A glass plate is attached to the upper electrode of a 10 cm diameter parallel plate electrode. After repeating the operation of deaerating the inside of the Pel jar to 10 torr or less and introducing argon eight times, the pressure inside the Pel jar was set to 0.1 torr with argon, and the pressure inside the Pel jar was set to 0.1 torr.
．． A high frequency of 56 MJ (z) was applied at the plasma output shown in Table 1 to generate argon plasma, and then a heating heater was heated to sublimate quinacridone. Quinacridone monomer was supplied into the plasma for 5 seconds by a monomer supply shutter. Then, a plasma polymerized film of quinacridone was formed on ITO glass.
第１表に通常の真空蒸着法で得られた蒸Ｗ膜の結果も示
す（Ｅｘｐ Ｎｏ、 ５ ）。真空蒸′４帳はモノマ
ーと同じ赤色を示し、爪でこすって容重にはがれ、又硫
酸にも容易に溶解するなど化学的、機械約６こ極めて弱
いものであった。これに対し、本発明のプラズマ重合膜
はやや黄味を帯びているが、５ｇＭ１ｔ察でも平滑な膜
であり、又マサツ抵抗性、硫酸不溶性も、蒸着膜よりす
ぐれていた。Table 1 also shows the results of the evaporated W film obtained by the usual vacuum evaporation method (Exp No. 5). The vacuum-steamed product showed the same red color as the monomer, peeled off when rubbed with a fingernail, and was easily dissolved in sulfuric acid, indicating that it was extremely weak chemically and mechanically. On the other hand, although the plasma polymerized film of the present invention had a slight yellowish tinge, it was a smooth film even when measured at 5 gM1t, and its mass resistance and sulfuric acid insolubility were also superior to that of the vapor-deposited film.
第 １ 表Table 1
第１図は本発明のキナクリドンプラズマ重合膜を製造す
るのに使用したペルジャー反応器であり、高周波電源（
１）、真空排気系１５）、冷却装置ａ１）、及び電極（
３）、 （９）、七ツマ−（６）、モノマー加熱用フィ
ラメント（４）、シャッターｔｔｃＪｂプラズマ重合用
基板＋８）を内蔵したプラズマ反応容器（２）等よりな
る。
第２図のムはキナクリドンの真空ｇ 、ｆｆ ｌ１ｆｉ
、ＢとＣは２０Ｗ、１００Ｗのプラズマ出力で重合した
時のプラズマ重合膜のＩＲ吸収スペクトルを示す。
第３図のａはキナクリドンの真空蒸着膜、ｂとＣは２０
Ｗ、１００Ｗのプラズマ出力で重合した時のプラズマ重
合膜の電子スペクトルを示す。
噸珊命 ゞ
第３図
浪畏（ｎｍ）
手続補正書（方式）
昭和６３年７月１９日
昭和６２年特許願第 ４５００８号
２、発明の名称
キナクリドンのプラズマ重合薄膜
３、補正をする者
事件との関係 特許出願人
住所 東京都墨田区墨田五丁目１７番４号〒５３４
大阪市部島区友淵町１丁目５番９０号鐘紡株式会社特許
部
電話（０６）９２１−１２５１
５、補正の対象
明細書の「図面の簡単な説明」の欄
６、補正の内容
（１）明細書第１０真下から３行に記載の「第２図のＡ
は」を「第２図はキナクリドンの各種薄膜のＩＲ吸収ス
ペクトルであり、Ａは」と訂正する。
（２）明細書第１１頁１行に記載の「第３図のａは」を
「第３図はキナクリドンの各種薄膜の電子スペクトルで
あり、ａは」と訂正する。
以上Figure 1 shows the Pelger reactor used to produce the quinacridone plasma polymerized film of the present invention, and shows a high-frequency power source (
1), vacuum exhaust system 15), cooling device a1), and electrode (
3), (9), a plasma reaction vessel (2) with a built-in seven magnet (6), a monomer heating filament (4), a shutter ttcJb plasma polymerization substrate +8), etc. The mu in Figure 2 is the vacuum g of quinacridone, ff l1fi
, B and C show IR absorption spectra of plasma polymerized films when polymerized at plasma outputs of 20 W and 100 W. In Figure 3, a is a vacuum-deposited film of quinacridone, b and C are 20
2 shows an electron spectrum of a plasma polymerized film when polymerized with a plasma output of 100 W. Kansan Mikoto ゞFigure 3 (nm) Procedural amendment (method) July 19, 1988 Patent application No. 45008 of 1988 2, title of invention Plasma polymerized thin film of quinacridone 3, person making amendment case Relationship with Patent applicant address: 5-17-4 Sumida, Sumida-ku, Tokyo 534
Patent Department, Kanebo Co., Ltd., 1-5-90 Tomobuchi-cho, Bejima-ku, Osaka Tel: (06) 921-1251 5. Column 6, "Brief explanation of drawings" of the specification subject to amendment, Contents of amendment (1) ) “A in Figure 2” written in the 3rd line from the bottom of No. 10 of the specification
``A'' is corrected to ``Figure 2 shows the IR absorption spectra of various thin films of quinacridone, and A is''. (2) "a in Figure 3" written in line 1 of page 11 of the specification is corrected to "Figure 3 shows the electronic spectra of various thin films of quinacridone, and a is". that's all
Claims (4)
のプラズマ重合薄膜。(1) A plasma-polymerized thin film of quinacridone that is solvent-insoluble and has photoelectric conversion ability.
載の薄膜。(2) The thin film according to claim 1, wherein the surface of the thin film is smooth.
とに２つの電子スペクトル吸収を有する特許請求の範囲
第１項記載の薄膜。(3) Thin film thickness is 490-510nm and 540-560nm
2. A thin film according to claim 1, which has two electronic spectral absorptions.
た時の光電変換能が少なくとも１×１０＾−＾５％であ
る特許請求の範囲第１項記載の薄膜。(4) The thin film according to claim 1, which has a photoelectric conversion capacity of at least 1×10^-^5% when irradiated with tungsten light of 100 mw/cm^2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4500887A JPS63308036A (en) | 1987-02-26 | 1987-02-26 | Plasma-polymerized thin film from quinacridone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4500887A JPS63308036A (en) | 1987-02-26 | 1987-02-26 | Plasma-polymerized thin film from quinacridone |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63308036A true JPS63308036A (en) | 1988-12-15 |
Family
ID=12707343
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4500887A Pending JPS63308036A (en) | 1987-02-26 | 1987-02-26 | Plasma-polymerized thin film from quinacridone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63308036A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101866797A (en) * | 2010-07-16 | 2010-10-20 | 中国科学院长春光学精密机械与物理研究所 | Preparation method of anode screen in field emission display device |
-
1987
- 1987-02-26 JP JP4500887A patent/JPS63308036A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101866797A (en) * | 2010-07-16 | 2010-10-20 | 中国科学院长春光学精密机械与物理研究所 | Preparation method of anode screen in field emission display device |
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