JPS61139075A - Manufacture of photoelectric conversion element - Google Patents

Abstract

PURPOSE:To enable mass production and the increase of an area by setting the relationship of a work function. CONSTITUTION:Thin semitransparent electrodes E1 are shaped continuously onto a light-transmitting plastic film at intervals in the width direction by layers consisting of a metal M1 (a work function phiM1). Layers mainly compris ing an organic photoconductive pigment (a work function phiS) are formed onto the electrodes E1 continuously or intermittently through application, thus shaping semiconductor layers S. Layers composed of a metal M2 (a work function phiM2) are formed onto the semiconductor layers continuously or intermittently, thus shaping electrodes E2. Lead wires for forming circuits to the electrodes E1 and the electrodes E2 are connected and shaped from sections where the electrodes E1 and the electrodes E2 are not crossed and superposed. phiM1<phiS<phiM2 or phiM1>phiS>phiM2 holds in the relationship of the work functions at that time. A junction with a metal having a small work function represents a rectifier junction on a P-type semiconductor, a junction with a metal having a large work function represents the rectifier junction on an N- type semiconductor, and the side brought to the rectifier junction is used as a front electrode.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photoelectric conversion element having an organic semiconductor layer.

Recently, research and development of photoelectric conversion elements using organic materials has been actively conducted in various fields because of the potential for lower costs and the possibility of increasing the area. Most of them are of the Schottky barrier type, which utilize rectifying contact between an organic material and a metal with a large difference in Fermi level (difference in work function).

Due to its operating principle, it is desirable that the semiconductor layer in a Schottky barrier type photoelectric conversion element be thin. Furthermore, in order to allow light to enter from the side where the barrier is formed, it is preferable that the so-called front electrode be as thin as possible.

In other words, light passing through the front electrode is absorbed by the semiconductor layer, and carriers are generated in the barrier layer formed by the contact between the semiconductor and the metal forming the front electrode.For example, holes pass through the semiconductor layer and flow to the outside. However, as the thickness of the semiconductor layer increases, the resistance increases accordingly, which is disadvantageous.

Therefore, when attaching a lead wire to an electrode and extracting photovoltaic power, if the lead wire is attached to the area where two electrodes cross and overlap, the conductive paint used for adhesion may seep in, mechanical load, etc. The comrades become short-circuited and photovoltaic power cannot be extracted. Looking at the shapes of photoelectric conversion elements that have been previously reported in literature (e.g., Vacuum Vol. 26, No. 1, Yamashita et al., IEEJ Transactions A, Vol. 101, No. 6, Kudo et al.), the substrate is like a slide glass. Using a small piece, 172
After one electrode EL is provided on the same area while masking or provided on the entire surface, it is etched or mechanically removed.
It forms parts with and without electrodes. Then, a semiconductor layer S is provided thereon, and another electrode is provided,
The lead wires are glued to prevent short circuits between the electrodes.

Although there is essentially no problem with this formation, it is a method that can only be adopted in batch production, and variations in quality are unavoidable. Also, it is not suitable for mass production or large-area production.

The present invention was made to solve the drawbacks of the conventional method, and is suitable for continuous mass production, has constant quality, is easy to perform post-processing, and can be easily expanded to a large area. The purpose of the present invention is to provide a method for manufacturing a photoelectric conversion element.

1-1 The present invention has been made as a result of intensive research to achieve this objective. (a) Metal M2 on a translucent plastic film
(Figure 1-a); (b) forming an organic photoconductive layer on the electrode E; A step of forming a semiconductor layer S by continuously or intermittently providing a layer containing a pigment (work function φS) by coating (Fig. 1-b); Function φMz
) to form the electrode E2 by continuously or intermittently providing the layer (FIG. 1-c); and (d) connecting lead wires for forming a circuit to the electrode E1 and the electrode E2 to the electrode E1 and the electrode E2. E2 has a step of connecting and connecting from the non-overlapping portions where E2 intersects and is not overlapped, and the work function relationship is φM, <φS, φM2 or φM,
It has been found that the above object can be achieved by providing a method for manufacturing a photoelectric conversion element characterized in that >φS>φM2.

Examples of the substrate used in the present invention include plastic films with good light transmission, such as polyethylene film, polypropylene film, polyvinyl chloride film, polyliquefied vinylidene film, polycarbonate film, polyester film, acetate film, and polyamide film. .

Next, a metal, an alloy, or a metal oxide having a work function φM1 is continuously deposited in a translucent manner at intervals in the width direction by vapor deposition, sputtering, etc. to form an electrode E, which is used as a front electrode.

Next, one type or several types of organic pigments are dispersed or dissolved in a solvent together with a binder if necessary, and applied onto the electrode E1 by an appropriate coating method and dried to form a semiconductor layer.

Examples of organic pigments include CI Pigment Blue 25.
[Color Index (CI) 21180], C.I. Pigment Red 41 (CI21200), C.I. Gid Red 52 (CI45100), C.I. Basic Red 3 (CI45210), as well as azo pigments with carbazole bone cores (Japanese Patent Laid-Open No. 53-95033) (described in the official publication), an azo pigment with styrylstilbene bone core (
(described in JP-A No. 53-138229), azo pigments having triphenylamine bone cores (described in JP-A-53-1325)
47), an azo pigment having a dibenzothiophene bone core (described in JP-A No. 54-21728), an azo pigment having an oxadiazole bone core (described in JP-A-54-1988)
2742), an azo pigment having a fluorenone bone core (described in JP-A-54-22834), an ab pigment having a bisstilbene bone core (JP-A-54-177)
33), an azo pigment having a distyryloxadiazole core (described in JP-A-54-2129), an azo pigment having a distyrylcarbazole core (described in JP-A-54-17734), ), trisazo pigment with carbazole bone core (Japanese Patent Application Laid-Open No. 57-195767
Publication No. 57-195758), and CI Pigment Blue 16 (CI74100).
Phthalocyanine pigments such as Sea Eye Butt Brown 5
(CI73410), Sea Eye Bat Die (CI73
Indigo pigments such as 030), Argo Scarlet B (
Violet Co., Ltd.), Indance Lens Scarlet R (
Bayer company! Perylene pigments such as I) are effective.

As a binder, various polymeric materials such as polystyrene, styrene-acrylonitrile copolymer, styrene-acrylonitrile copolymer, etc.
Butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyarylate resin, polyvinylidene chloride, cellulose acetate, ethyl cellulose, polyvinyl butyral, polyvinyl formal,
Polyamide, poly-N-vinylcarbazole, polyvinyltoluene, acrylic resin, polycarbonate, silicone resin, epoxy resin, melamine resin, urethane resin,
Thermoplastic resins such as phenolic resins and alkyd resins.

Thermosetting resins, starch, glue, natural products such as casein, etc. may be used alone or in combination.

Examples of solvents include hydrocarbons such as benzene, toluene, and xylene; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethers such as tetravitrofuran and dioxane; and esters such as ethyl acetate, propyl acetate, and butyl acetate. Chlorinated hydrocarbons such as methylene chloride, diliquefied ethylene, 1,1,2-trichloroethane, carbon tetrachloride, monochlorobenzene, 0-° dichlorobenzene, n-propyl alcohol,
Isopropyl alcohol.

Preferably, alcohols such as n-butyl alcohol and isobutyl alcohol are used.

The thickness of the semiconductor layer is 10 μm or less, preferably 2.5 μm.
The following are appropriate.

As a coating method, a reverse roll coater, a gravure coater, a kiss roll coater, a curtain coater, etc. are suitable.

Next, a metal M2 having a work function φM2 is deposited on the semiconductor layer,
It is provided by sputtering, etc., and is used as the electrode E2 as a back electrode. Lead wires for forming a circuit on the electrode E and the electrode E2 are connected by conductive paint or the like from the part where the electrode E1 and the electrode E2 cross and do not overlap.

The connection from the electrode E may be made after removing the semiconductor layer S with a solvent or the like to expose the electrode E1, depending on the case. The relationship between the work functions is φM×φS〈φM2 or φM i＞φS〉φM2, and the organic pigment used is P
In the case of a type semiconductor, the electrode material is selected so that the relationship φM1<φS<φM2 is satisfied. Further, when the material pigment used is an N-type semiconductor, the electrode material is selected so that the relationship φM l >φS>φM2 is satisfied. In the case of a P-type semiconductor, the junction with a metal with a small work function is a rectifying junction, and in the case of an N-type semiconductor, the junction with a metal with a large work function is a rectifying junction, and the side to which the rectifying junction is made is used as a front electrode. As a metal material (electrode material), M g r A Q e M
n * F e + Co e N x eCu, Z
n, Nb, Mo, Pd* Agt P ttA u p
ITO (indium-tin oxide) and the like are preferred.

Examples are shown below to further specifically explain the present invention, but the present invention is not limited thereto.

Example A polyethylene terephthalate film with a thickness of 75 μm was used as the base, and aluminum with a purity of 99.99% was used at a wavelength of 5.
A front electrode was formed by vacuum deposition with a width of 100 mm and an interval of 50 mra so that the transmittance at 60 nm was 30%, and the film was wound onto a roll. Next, 2 parts of a disazo pigment with the following structural formula, which is a P-type semiconductor, 1 part of butyral resin (■ Sekisui Chemical's S-LEC BX-1), and 2 parts of latrahydrofuran.
Place 7 parts in a ball mill pot and mill for 24 hours.
Transfer the mill base to a container, dilute it with tetrahydrofuran to a concentration of 1.5% by weight, stir to prepare a semiconductor layer coating solution, and apply it on the aforementioned front electrode and insulating layer using a two-roll dip coater. A semiconductor layer having a thickness of approximately 0.5 μm was formed.

Disazo Pigment Next, gold with a purity of 99.99% was vacuum deposited on the semiconductor layer to provide a back electrode. The photoelectric conversion element created as above was cut out to an appropriate size, and lead wires (copper wires were used) were glued to the parts where the electrodes crossed and did not overlap using silver paste, and the light intensity was 10 μW. /d white tungsten light was irradiated from the front electrode side, and the conversion efficiency was determined to be 0.11%. The photoelectric conversion element manufactured by this method can be easily turned into a device with any area and shape.

effect As described above, according to the method of the present invention.

Continuous production is possible, making mass production and large area possible.

[Brief explanation of the drawing]

1-c to 1-c are simplified diagrams showing the manufacturing process of the present invention. 1... Translucent plastic film base. S: Organic semiconductor layer, M: Front electrode metal layer. M2... Back electrode metal layer, A... Continuously coated part, B... Intermittently coated part Procedural amendment dated February 22, 1985 1, Case indication 1982 Patent Application No. 261630 2 , Name of the invention Method for manufacturing photoelectric conversion elements 3, Relationship with the case of the person making the amendment Patent applicant 1-3-6 Nakamagome, Ota-ku, Tokyo (674) Ricoh Co., Ltd. Representative Hama 1) Hiro 4, Agent 5, Subject of amendment 6, Contents of amendment (1) Page 5, line 18 of the specification: "Polyliquefied vinylidene" is corrected to "polyvinylidene chloride." (2) Same, page 9, line 1: "Diliquefied ethylene" is corrected to "r-dichlorinated ethylene." (3) Same, page 11, line 14: Corrected. that's all

Claims (1)

[Claims] 1. In the method for manufacturing a photoelectric conversion element, (a) a metal M_1 (
Step of continuously forming a thin translucent electrode E_1 by spacing layers with work function φM_1) in the width direction; (b) forming an organic photoconductive pigment (work function φS) as a main component on the electrode E_1; step of forming a semiconductor layer S by continuously or intermittently providing a layer of metal M_2 (work function φM_2) on the semiconductor layer;
) forming the electrode E_2 by continuously or intermittently providing a layer; and (d) forming a lead wire for forming a circuit on the electrode E_1 and the electrode E_2 so that the electrode E_1 and the electrode E_2 intersect and overlap. It has a process of connecting and installing from a part that does not exist,
A method for manufacturing a photoelectric conversion element, characterized in that the relationship between the work functions is φM_1<φS<φM_2 or φM_1>φS>φM_2.