JPH067589B2 - MSM or MIS type element using phthalocyanine derivative thin film as semiconductor layer and method for manufacturing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to an MSM type element comprising a conductive material layer having a large work function, a semiconductor layer, and a conductive material layer having a small work function, which are laminated in this order, The present invention relates to a MIS-type element in which a conductive material layer having a large function, a semiconductor layer, an insulating layer, and a conductive material layer having a small work function are laminated in this order, and a manufacturing method thereof.

[Conventional technology]

Metal having a large work function (M _A) and poly (acetylene) between small metal (M _B) work function, poly (diacetylene), poly (pyrrole), poly etc. (thienylene) organic semiconductor (S) M incorporating a thin layer of insulator (I) MSM type comprising across the thin layer, or even between S and M _B
Many IS-type devices have been devised ["Fixics of Semiconductor Devices" Second Edition, SM Suze, John Willie & Sun, New York (1
981): “Physics of Semiconductor Devices” 2nd E
d., SMSze, John Wiley & Sons, NY (1981), “Synthetic Metals (Chemical Special Issue 87)” Shirakawa and others, Kagaku Dojin (1980)
R. C. West, N.W. J. Astor, "CRC Handbook of Chemistry and Physics, CRC Press, Cleveland (1979), 59th.
Edition, E-81: RCWest, NJAstle Ed., "CRC Handbo
ok of Chemistry and Physics ”CRC Press, Cleaveland
(1979), 59th Ed., E-81, M. Ozaki et al., Applied Physics Letters: M. Ozaki et al., Appl. Phys. L
ett 35 3 (1979)]. However, in general, uncertainties due to the structure of the S layer and the method of manufacturing the device are remarkable, and none of them has been put to practical use. For example, these S layer, gas-phase polymerization in the normal M _A substrate, but is prepared by solid phase polymerization or electrolytic oxidation polymerization, the microstructure because of inflow and outflow, etc. during polymerization of the telescopic or an electrolyte ion It is in the form of a fibril with many fibrils and peaks / valleys, and is generally porous. Therefore, if the S layer thickness is not large, when fixing the M _B layer by vapor deposition, sputtering, etc., the M _B particles go into the fine holes,
It is easy for M _A and M _B to directly conduct and lose the function as an element. These organic semiconductors, chemical doping, when subjected to processing in the electrochemical doping, etc., such as poly (acetylene) / about 10 2 ^{S /} cm iodine doped poly (pyrrole) / iodine doped with about 10 ² S / Cm, like
Provides high conductivity, but very low conductivity in the undoped state. Moreover, the S layer subjected to the doping treatment is M _A , M _B
When combined with, the doping _{agent, M} A / S and _M B / S, proceeds particularly corrosion _M B / S interface, stability over time is remarkably poor. Because it has generally these S layer is used in low conductivity undoped state, remarkably high element in the resistance to increase the S layer to prevent underrun described above the M _B particles, Kyoseru practical It cannot pass as much current. Furthermore, the above-mentioned S layer has severe irregularities on the film surface as described above. Therefore, in the MSM type device,
Impurity levels are likely to occur at the important S / M _B interface forming a Schottky junction, and as a result, the rectification ratio of the device, the diode characteristics, etc. are significantly impaired. For example, the diode parameter for poly (acetylene) is at most 1.9, and other values are almost the same, and it can be said that it is far from the ideal state of 1.0. In the MIS type element, since the I layer needs to be thin enough to expect a tunnel effect (about 20Å), if the surface of the S layer is highly uneven, the I layer will be significantly disturbed. Therefore, the characteristics of the device are impaired.

When the resistance of the S layer is large and the unevenness is severe, in other words, when the local film thickness is not constant, a local large current flows in a portion having the smallest S layer thickness when a current is passed. . Therefore, in such a case, there is a drawback that irreversible destruction of the thin film is likely to occur.

The phthalocyanine derivative is an organic p-type semiconductor having a wide maximum absorption in the visible region to the near infrared region, and is chemically stable, and thus is suitable as an electronic material. However, general (metal) phthalocyanine is concentrated sulfuric acid, heat DM
It only slightly dissolves in F and the like, and the thin film formation must rely on thermal evaporation or the like. Therefore, since the fine structure is polycrystalline and the surface of the film is highly uneven, good element characteristics cannot be obtained when the Schottky junction or the like is performed for the same reason as described above. There is an example of dissolving lithium phthalocyanine in a special multi-component solvent, applying it to the Langmuir-Blodgett method to form a thin film at the air / water interface, and then transferring it to a substrate to form an element (eg S .Ba
ker et al., Thin Solid Films, 99 53 (1983).
Etc.), the state of the thin film surface is not clear, and since lithium phthalocyanine is hydrolyzed when it contacts the water interface in this method, only a thin film of phthalocyanine containing no metal is obtained.

[Object of the Invention]

Therefore, it is an object of the present invention to use conventional MSM or MIS.
It is an object of the present invention to provide a novel MSM or MIS type element and its manufacturing method which do not have the drawbacks of the type element.

[Structure of Invention]

The present inventor has completed the present invention by finding that the above object can be achieved by using a thin film made of a specific phthalocyanine derivative as a semiconductor layer. That is, the present invention provides an MSM type element formed by laminating a conductive material layer having a large work function, a semiconductor layer, and a conductive material layer having a small work function in this order, or a conductive material layer having a large work function, a semiconductor layer, In a MIS type element formed by laminating an insulating layer and a conductive material layer having a small work function in this order,
The MSM or MIS type device is characterized in that a phthalocyanine derivative thin film represented by the following formula (1) is used as the semiconductor layer.

However, R is a linear or branched hydrocarbon group having 3 to 25 carbon atoms, Me is H ₂ or magnesium or a transition metal ion, and the substitution position of the —OR group is 5 to the isoindoline group of the above formula. Or 6-position.

The phthalocyanine derivative of the formula (1) has various properties such as the chemical stability peculiar to the general (metal) phthalocyanine described above, the property as a p-type semiconductor, and a wide visible to near infrared absorption band. Not only that, but any phthalocyanine complex of any central metal species within the range described above is soluble in at least chloroform. Further, the phthalocyanine derivative of the formula (1) has a melting point, although the temperature varies depending on the central metal species. Therefore, by utilizing these properties, a semiconductor layer with an extremely smooth surface can be easily formed by cast film formation, spin coating, Langmuir-Blodgett, melt-casting method, etc. Elements can be created. As described above, the present invention provides a simple MSM or MIS type device having excellent characteristics and a manufacturing technique thereof.

The conductive material M _A having a large work function used in the present invention has a sheet resistance of 30 Ω / sq. The following are indium tin oxide, graphite, glassy carbon, arsenic, palladium, tellurium, rhenium, iridium, platinum, gold, rhodium, ruthenium, selenium and germanium.

Further, examples of the conductive material M _B having a small work function include lithium, beryllium, sodium, magnesium, aluminum, potassium, calcium, scandium, titanium, manganese, zirconium, gallium, yttrium, niobium, cadmium, indium, antimony, and lanthanides. , Thallium, lead.

The insulating layer used in the present invention is preferably a metal salt of a straight chain saturated fatty acid having 16 to 22 carbon atoms, particularly a cadmium salt, a mercury salt or an alkaline earth metal salt.

In the MSM or MIS type element of the present invention, a semiconductor layer made of a phthalocyanine derivative thin film represented by the formula (1) is provided on a substrate made of a conductive material having a large work function, and an insulating layer is provided on the semiconductor layer. It can be manufactured by forming a conductive material layer having a low work function with or without providing.

Further, the semiconductor layer composed of a phthalocyanine derivative, for example, by transferring a monomolecular film of the phthalocyanine derivative onto the substrate by a vertical dipping method or a horizontal deposition method, or by applying a volatile organic solvent solution of the phthalocyanine derivative on the substrate, It can be formed by evaporating the solvent or alternatively by melt casting the phthalocyanine derivative on the substrate.

The insulating layer can be formed, for example, by transferring a monomolecular film of a linear fatty acid metal salt onto a substrate by a vertical dipping method or a horizontal attachment method.

The phthalocyanine derivative used in the present invention is, for example,
4-nitrophthalonitrile represented by the formula (2) and R-OH (R
Is as described above) To obtain the corresponding 4-alkoxyphthalonitrile,
Furthermore, it is reacted with ammonia gas using sodium trimethoxide in dehydrated methanol as a catalyst to form a diiminoisoindoline intermediate (formula (3)), and then 2-dimethylamino in the presence or absence of a salt of magnesium or a transition metal. It is obtained by ring-closing condensation in ethanol under reflux of boiling point.

As described above, the MSM or MIS type device of the present invention is obtained by casting or spin-coating the thus obtained phthalocyanine derivative on a conductive substrate having a large work function from a volatile solvent solution. The monomolecular film obtained by dripping the solution on the water surface and evaporating the solvent is repeatedly transferred onto the above-mentioned substrate by the vertical dipping method or the horizontal attachment method, or the film thickness of the phthalocyanine derivative is 20 Å ~ 1 μm by melt casting. And the monomolecular layer of a straight chain saturated fatty acid having 16 to 22 carbon atoms, such as a cadmium salt, a mercury salt or an alkaline earth metal salt, is transferred by the vertical dipping method or the horizontal deposition method as described above. After being taken, it is manufactured by coating a conductive material having a small work function by vapor deposition, sputtering or the like.

The phthalocyanine derivative of the formula (1) is insoluble when R has 2 or less carbon atoms and difficult to synthesize when R has 26 or more carbon atoms. And as long as it is within the range described above, it is soluble in at least chloroform regardless of the central metal species.
In particular, when R has 8 or more carbon atoms, it becomes all soluble in general low dielectric constant organic solvents except DMF, DMSO, hexamethylphosphoric triamide, and alcohols having 4 or less carbon atoms, and even soluble in petroleum ether. . By utilizing this solubility, a semiconductor layer of a phthalocyanine derivative can be easily formed by casting a film from a chloroform solution or spin coating. The film-forming solvent preferably has a boiling point in the range of about 60 to 80 ° C., and examples thereof include chloroform, THF, benzene, ethane dichloride and the like. Of these, chloroform is most preferred. In the cast film formation, when the concentration of the phthalocyanine derivative is 10 mg / ml or more, or when the solubility is less than this, a saturated organic solvent solution is prepared,
It spreads on the above-mentioned substrate within the range of 30 ° C, starts from the vapor pressure of 1/2 of the saturated vapor pressure of the organic solvent, gradually reduces the amount of solvent vapor in the air, and gradually evaporates the solvent, Finally, vacuum drying is performed. This process is preferably performed very gently, eg R = n-propyl, Me = copper, 10
1 ml of a mg / ml chloroform solution has a surface area of 100 cm ^2.
When it is spread on indium tin oxide glass (hereinafter abbreviated as “ITO”), it takes about 3 days to reach vacuum drying at 20 ° C. If this process is carried out rapidly at a high temperature, a porous film is formed, which is unsuitable. The semiconductor layer thin film formed by this method is relatively thick and has a thickness of several hundred Å to 1 μm. In the spin coating, the phthalocyanine derivative of the formula (1) is made into a chloroform solution of about 1 mg / ml to 0.5 mg / ml and dropped on the center of the rotated substrate,
When the solvent is evaporated, a thin film is formed. The substrate rotation speed and the development temperature depend on the type of phthalocyanine derivative, the dropping amount,
Depending on the area of the substrate, for example, R = n-propyl, M
When 500 μ of a 1 mg / ml chloroform solution of e = copper is spread on the ITO surface having a surface area of 100 cm ² , the substrate temperature is preferably 30 ° C. and the substrate rotation speed is about 2000 rpm.
The semiconductor layer thin film formed by this method is about 50 to several hundred Å
Is the range.

1.0 mg / m of the phthalocyanine derivative of the formula (1) to 0.
Chloroform solution of about 5 mg / ml, typically 4
A monolayer film of a phthalocyanine derivative obtained by adding 0 to 500 μl onto a water surface of 2500 cm ² to evaporate the solvent, and then moving a sill plate installed at the air-water interface to obtain a surface pressure of 5 to 30 dyn / cm. Repeat the operation of pulling down the above-mentioned substrate installed vertically to the water surface until it is submerged in an appropriate amount and then lifting it into the air (this method is abbreviated as vertical immersion method), or installed parallel to the water surface. The accumulated film-like semiconductor layer is formed by lowering the above described substrate until it comes into contact with the above-mentioned monolayer film, and then repeating the pulling operation (this method is abbreviated as horizontal attachment method). If the vertical velocity of the substrate at this time is sufficiently low, a semiconductor layer having an extremely excellent accumulated state of the film and orientation in the plane direction of the film can be obtained. However, considering the operation performance, the vertical speed may be 0.5 mm / min or less, and is in the range of 0.5 to 0.2 mm / min in the embodiment of the present invention. The state of existence of the phthalocyanine derivative of formula (1) at the air / water interface is schematically represented in the accompanying drawings. When this is transferred to the substrate, the X film on which the ether oxygen, which is a hydrophilic group, and the phthalocyanine ring are located, and the Z film, on the contrary, where the R group, which is a hydrophobic group, is located toward the substrate surface. To X
Three types of Y films, which are formed by repeating the arrangement of both the Z-type and the Z-type, are conceivable. If the cumulative number is about 5 or less in the vertical dipping method, an X film or a Z film is easily formed, and the Y film is formed as the cumulative number increases. However, which of the X-type and the Z-type when the cumulative number is small largely depends on the properties of the substrate and the types of Me and R groups.

The cumulative number of transitions from the X-type or Z-type to the Y-type due to the increase in the cumulative number also largely depends on the nature of the substrate and the types of Me and R groups.

In the horizontal deposition method, only the Z film is formed in principle.

In principle, the cumulative film-like semiconductor layer formed by the vertical dipping method or the horizontal deposition method can be formed from a monomolecular layer film, that is, the thickness of the molecule, and can be up to the mm order if the accumulation is repeated. However, considering the operation performance of the element formation which will be described in detail later and the accumulation method described above, up to about 1 μm is appropriate. Further, regardless of the R groups, if: the average film thickness 20 Å, it is considered to be due to surface irregularities of the substrate, when forming the MSM element in combination with M _B,
M _A and M _B are in direct conduction and no characteristic function appears. The average film thickness of 20Å or less, like in MIS type device in combination with I and M _B is believed to result in greatly disturbance of I layer, it does not appear again characteristic function to the MIS type element. The film thickness of about 20Å is 4 when R = n-propyl.
When R = n-pentaeicosanyl, it corresponds to the cumulative number 1.

The cumulative film-like semiconductor layer formed by the vertical dipping method or the horizontal attachment method is characterized in that the phthalocyanine derivative represented by the formula (1) of the constitutional unit is in a microscopic molecular orientation state and the surface is smooth. . Therefore, when a hetero-adhesion is formed, an impurity level is unlikely to occur at the interface, and a current flows evenly in any part of the film, so that the breakdown voltage is high, a large current can be applied, the rectification ratio and the diode parameter. It can exhibit high functionality such as excellent.

The phthalocyanine derivative of the formula (1) has a melting point near about 400 ° C., although it varies slightly depending on the central metal species, and becomes a liquid substance having a stable viscosity in an inert atmosphere such as nitrogen or argon. However, since the decomposition starts at a temperature about 50 ° higher than the melting point, the semiconductor layer can be melt cast on the above-mentioned substrate by operating in an inert atmosphere in the temperature range from the melting point to the decomposition point. In this case, like spin coating, a liquid substance having a melting point or higher may be dropped onto the center of the substrate that rotates at a high speed, but rather, a predetermined amount of powdery solid substance may be placed on the center of the substrate while the rotation is stopped, and The method of gradually increasing the number of revolutions when it is heated to become liquid becomes easier to obtain a constant film thickness. The high-speed rotating substrate-liquid material dropping method is abbreviated as "drop rotation method" below, and the powdery solid material-melting-rotation method is abbreviated as "melt rotation method" below, and this abbreviation is used in Examples. . In both of these methods, the substrate rotation speed in the steady state is preferably about 5000 to 8000 rpm, and which value is set within this range depends on the dropping amount of the liquid substance, the powder solid substance installation amount, and the substrate area. During the rotation of the substrate, it is necessary to set the substrate temperature above the melting point and below the decomposition point. When the liquid semiconductor layer is developed, it is preferable to stop the rotation as gently as possible and quench it. However, as will be described later, the device of the present invention is used as an electrochromic display device when R is a phthalocyanine derivative of a linear alkyl group having 12 or more carbon atoms in the formula (1) is used as a semiconductor layer. The slow cooling is preferable because the discotic liquid crystal has a better alignment state. In the case of rapid cooling, typically, cold CO ₂ gas just generated from dry ice is wiped onto the back surface of the substrate. During slow cooling, the substrate temperature is controlled by a heat source from the outside,
The temperature is lowered at about 10 ° C./minute. In the case of rapid cooling, the structure of the semiconductor layer is amorphous, and the surface is extremely smooth except for rough undulations, which is useful for manufacturing rectifying devices, field effect transistors, etc. that utilize the junction characteristics of MSM or MIS type devices. It is suitable and can realize a good situation in terms of rectification ratio and diode parameters. On the other hand, in the case of slow cooling, particularly when a straight chain alkyl group phthalocyanine derivative having R 12 or more carbon atoms in the formula (1) is used, a discotic liquid crystal having a polarizing property is obtained, and R is an alkyl group C 11 or less. In this case, crystal growth was observed in a part or most of the area (this tendency is greater as the carbon number is smaller), and in any case, fine irregularities are observed on the surface. Therefore, in this case, the junction characteristics are not always good, and the diode parameter exceeds 1.9, for example.

In both the dropping rotation method and the melting rotation method, the film thickness of the semiconductor layer is about several thousand to 1 μm.

The shape of the conductive material substrate M _A having a large work function is not particularly limited as long as it is a thin plate. However, particularly when a semiconductor layer having a thickness of 100 Å or less is formed by the vertical dipping method or the horizontal deposition method, the plate thickness is preferably 2 mm or less, and 1 to 0.
5 mm is most suitable. Further, since the roughness of the substrate surface affects the film thickness accuracy of the semiconductor layer formed thereon, it is desirable that the roughness be as smooth as possible. For example, ITO
Then, a nesa layer was formed on the surface of a flat glass by a normal CVD method, a pyrolytic graphite had a fresh basal cleavage surface, and a glassy carbon was previously polished with 3 to 1 μm of alumina powder. The substrate of the present invention is one having a surface polished by laminating the surfaces while rotating each other at about 2000 to 5000 rpm, and for other metal species, glass or a flat plate surface of the metal which is a smooth metal surface by ordinary high frequency sputtering. Is suitable as Of these, only for pyrolytic graphite, the film thickness of the semiconductor layer formed on it is 2000 Å or more, and if it is less than that, the bare surface of the substrate which is not covered by the semiconductor layer is recognized due to the unevenness of the substrate surface. However, it cannot be used for the purpose of forming an element described later.

If M _A / S obtained as described above is coated with a conductive material M _B having a small work function, an MSM type element is obtained. These coating methods can be carried out by thermal vapor deposition for lithium, beryllium, sodium, magnesium, aluminum, potassium, calcium, and the other is by high frequency sputtering.

When M _B is coated on M _A / S, a monolayer of a straight chain saturated fatty acid having 16 to 22 carbon atoms such as a cadmium salt, a mercury salt or an alkaline earth metal salt is formed between S and M _B. If it becomes a MIS type element. The straight-chain fatty acid metal salt monolayer film is developed by the above-mentioned vertical dipping method or horizontal adhesion method. However, 1.0-0.5 mg / of the above-mentioned linear fatty acid
ml of chloroform solution was added dropwise to the water surface, and then 0.1 to 0.8 mmol / cadmium chloride, mercuric chloride and alkaline earth metal chloride were present in the aqueous phase,
As a result, a monolayer of the metal salt of the fatty acid is formed. The surface pressure at the time of forming these single layer films is about 15 to 25 dyn / cm, but 20 to 22 dyn / cm is most preferable.

〔The invention's effect〕

The MSM or MIS type element of the present invention is excellent in rectifying characteristics and diode characteristics, and particularly in the formula (1), R is 5 carbon atoms.
When the following phthalocyanine derivative having an alkyl group is used as a semiconductor layer, it is not destroyed even by a large current of several hundred mA / cm ² . Therefore, it can be used as a rectifying element such as a diode, a field effect transistor, or the like. Further, since the semiconductor layer made of the phthalocyanine derivative of the formula (1) has a wide absorption band in the visible region to the near infrared region, it can be used as a solar cell. Further, in the formula (1), when R is a straight-chain alkyl group having 12 or more carbon atoms, it becomes a discotic liquid crystal at the time of forming a semiconductor layer thin film, and the molecular orientation state is changed by applying a voltage, and the color tone is changed. Available as

〔Example〕

Next, the present invention will be described in more detail by reference examples and examples.

Reference Example 1 4-nitro-1,2-phthalonitrile (hereinafter abbreviated as NPN) 50 g (0.29 mol) and n-propyl alcohol 21 g (0.35 mol) were dissolved in 100 ml of dehydrated DMF and dried with CaCl _2. It was placed in a 300 ml four-necked flask equipped with a reflux tube with a tube and a nitrogen introduction tube, and 43,07 ml (0.29 ml) of 1,8-diazabicyclo [5,4,0] undecene- (7) was placed in a nitrogen atmosphere while stirring. Mol),
The reaction was carried out at 65 ° C for 6 hours. After cooling, the mixture is concentrated under reduced pressure at 40 ° C. or lower, an appropriate amount of chloroform is added, and the mixture is poured into 600 ml of water-cooled 6N-HCl to separate the chloroform phase.
The aqueous phase was extracted with 100 ml × 3 times of chloroform, combined with the above chloroform phase, and dried over anhydrous sodium sulfate,
After filtering and decolorizing the activated carbon, the solvent is concentrated under reduced pressure. After cooling, the yellow crystals (unreacted NPN) that precipitated were removed, and the mother liquor was further concentrated and recrystallized to give 53.0 g (9
3.4%) was obtained. As a result of the analysis, it was found to be the target 4-n-propoxy-1,2-phthalonitrile.

NMR (CDCl ₃ , δppm): Ha 7.1, 7.2
(1H), Hb 7.2 (1H), Hc 7.65,
7.7 (1H), Hd 4.3 (2H), He 2.2
(2H), Hf 1.3 (3H) IR (KBr tablet, cm ⁻¹ ): ν _φ-H 3100, 30
50, 3000, 2980,2950,2850, ν _C≡N 2550 put this thing whole amount above the same device, in dry methanol 200 ml, sodium methoxide 2g addition, 2 hours at room temperature while passing vigorous dry ammonia gas, boiling point reflux The reaction was allowed to proceed for 1 hour. The white precipitate formed after cooling was collected by filtration and vacuum dried to obtain 54.2 g (98.5%) of 5-propoxydiiminoisoindoline.

5-propoxydiiminoisoindoline IR (KBr tablet, cm ⁻¹ ): ν _NH 3400, ν _φ-H 3
100, 3045, 3000, 2980,2955,2850, appearance and [nu _CN 2250 of [delta] _NH 1640 is lost is this compound strongly hygroscopic, confirmed the disappearance of [nu _C≡N than IR, it was carried out by the appearance of [nu _NH and [delta] _NH.

5.2 g (25.6 mmol) of this product was dissolved in 20 ml of dehydrated 2-dimethylaminoethanol and refluxed at the boiling point for 6 hours in a dry nitrogen atmosphere. After cooling, methanol about 600
The resulting green precipitate was collected by filtration to obtain 2.3 g (48.2%) of a phthalocyanine derivative of the formula (1) in which R = n-propyl and Me = H ₂ .

FD mass spectrum: M / e = 747 (molecular weight 746.
87) Elemental analysis (wt%, calculated value in parentheses): C 71.22 (70.76), H 5.75 (5.6)
7) N 14.96 (15.00) visible absorption spectrum (CHCl ₃ nm, log in parentheses)
ε): 704.5 (5.06), 668 (5.0
0), 642 (4.66), 607 (4.44) 578
^sh , 558 ^sh , 390 (4.53) Reference Example 2 n-Eicosanol 1 instead of n-propyl alcohol
04.5 g (0.35 mol), diazabicyclo [5,
4,0] Undecene- (7) was replaced with 27 g (0.29 mol) of 4-methylpyridine, and 110.4 g (89.7%) of white waxy crystals were prepared in the same manner as in Reference Example 1. The target 4-eicosanoxy-1,2-phthalonitrile was obtained.

NMR (CDCl ₃ , δppm): Ha 7.1, 7.2
(1H), Hb 7.2 (1H), Hc 7.65,
7.7 (1H), α-CH ₂ 4.25 (2H), β-C
H ₂ 2.2 (2H), γ-CH ₂ 1.85 (2H), other CH ₂ 1.6 (wide, 32H) CH ₃ 1.3 (3H) IR (KBr tablets, cm ^-1 ). : CH ₂ stretching vibration band (280
0 to 3000), CH ₂ bending vibration band (around 1450), and the like.
It is very similar to 1,2-phthalonitrile.

The whole amount of this was reacted with NH ₃ gas in the same manner as in Reference Example 1 to obtain 109.1 g (95%) of the corresponding 5-eicosanoxidiminoisoindoline. Since this product has a strong hygroscopic property, it was found by IR (KBr tablet method) analysis that ν _NH 34
00, appearance of δ _NH 1640 cm ^-1 , and ν _C ≡ _N 2250 cm
^The structure was confirmed by the disappearance of ^-1 . It should be noted that it is very similar to the IR of 5-propoxydiiminoisoindoline except that the strength of the CH ₂ expansion or contraction vibration band described above is extremely large.

4.4 g (10 mmol) of this product was reacted in dehydrated 2-dimethylaminoethanol in the same manner as in Example 1 and treated in the same manner as in Example 1 to obtain R = n-eicosanyl in the formula (1) and Me = H. 1.8 g of phthalocyanine derivative of ₂ (4
2.3%) was obtained.

FD-mass spectrum: M / e = 1702 (molecular weight 17
00, 715) Elemental analysis (wt%, calculated value in parentheses): C 79.12 (79.10), H 10.71 (1
0.67), N 6.62 (6.59) visible absorption spectrum (CHCl ₃ nm, log in parentheses)
ε): 705 (5.06), 668 (5.00), 6
42 (4.66), 607 (4.45), 578 ^sh , 3
91 (4.54) Reference Example 3 Reference Example 1 in the presence of 4 g (about 40 mmol) of cuprous chloride.
The cyclization reaction described in the final stage of was carried out with the same charging and equipment. After cooling, the solvent was distilled off under reduced pressure, the solid was extracted with chloroform, washed with 50 ml of 0.01N hydrochloric acid three times, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. Φ10 × made with chloroform / methanol (40/1) mixed solvent
30 cm silica gel column (100-200 mesh)
Developed with the same solvent, collected the blue-green band of Rf = 0.45, concentrated under reduced pressure, dropped into methanol with stirring 1 while filtering with a glass filter (G4), and the resulting blue-green color The precipitate was collected. Analysis result, target formula
In (1), R = n-propyl, Me = copper (II) phthalocyanine derivative. The yield was 4.6 g (88.9).
%, But based on the diiminoisoindoline form).

FD-mass spectrum: M / e = 809 (Mw = 80
8.4) Elemental analysis (wt%, calculated values in parentheses, but for copper by atomic absorption spectrometry): C 64.92 (65.37), H
5.04 (4.99), N 13.91 (13.8)
6), Cu 7.90 (7.86) visible absorption spectrum (CHCl ₃ nm, log in parentheses)
ε): 682 (5.03), 616 (4.63), 5
67 ^sh , 381 (4.41) Reference Example 4 A cyclization reaction was carried out in the same manner as described in the latter part of Reference Example 2 except that 1.9 g (about 20 mmol) of magnesium chloride was allowed to coexist, and then Reference Example. Column treatment was performed in the same manner as in Example 3 to collect blue-green bands with Rf = 0.62, and reprecipitation treatment was performed in the same manner as in Reference Example 3 to obtain R =
4.2 g (97.5%) of a phthalocyanine derivative of n-eicosanyl and Me = magnesium (II) was obtained.

FD-mass spectrum: M / e = 1725 (Mw = 17
23.01) Elemental analysis (wt%, values in parentheses are calculated values, but magnesium is by atomic absorption spectrometry): C 78.11 (78.0)
7), H 10.42 (10.30), N 6.53
(6.50), Mg 14.07 (14.10) Visible absorption spectrum (CHCl ₃ nm, lo in parentheses)
g ε): 702 (5.07), 670 (4.98),
640 (4.60), 385 (4.45) As described above, by any one of the methods shown in Reference Examples 1 and 2,
The 4-alkoxy-1,2-phthalonitrile represented by (2) and the 5-alkoxydiiminoisoindoline represented by the formula (3) were synthesized and corresponded by the method shown in Reference Examples 1 and 2 or 3 and 4. A phthalocyanine derivative or a metal phthalocyanine derivative is synthesized. Table 1 of them,
It is summarized in Table 2.

Example 1 In the formula (1), the phthalocyanine derivative having R = n-propyl and Me = H ₂ is soluble in chloroform. 0.5 mg
/ ML solution, and commercially available ITO Nesa glass (10Ω / sq., 100cm ² thin disk) prepared by the ordinary CVD method.
Is rotated at 2000 rpm and centered at 50 at 30 ° C.
The solvent was evaporated by adding 0 μl dropwise and rotating for 5 minutes.
A stylus-type surface roughness tester revealed that a defect-free thin film with an average film thickness of about 220 Å was formed in the central area of about 50 cm ² , so a 3.5 × 5.0 mm slit was formed in this area. A mask having a large number of layers was applied, and aluminum was vacuum-deposited at 10 ⁻⁵ Torr to a film thickness of about 150 Å. IT
A contact point was provided on each of the O portion and the 3.5 × 5.0 mm aluminum vapor deposition portion to form an MSM type element. IT using a normal function generator-potentiometer galvanostat combination
The O-side was used as the working electrode terminal and the aluminum side was used as the counter electrode terminal, and a ramp wave was applied at a sweep rate of 1 mV / sec in the range of -10 to +10 V, and the current value was observed to create a voltage-current curve. As a result, the S thin layer of this phthalocyanine derivative has a p-type property and has an open circuit voltage (abbreviated as V _OC ).
0.75 V, closed circuit current (abbreviated as I _SC ) 1.3 nA / cm ² ,
It was found that the rectification ratio at 1 V was 1.45 · 10 ³ , and the diode characteristics were excellent at 1.6. Further, when the above electrical measurement was performed under white light, V _OC 0.77
V, I _SC 850 nA / cm ² , film factor (abbreviated as ff) 0.32, photoelectric conversion efficiency (abbreviated as η) 2.5 · 10 ^-2
It was shown that it could be a% photodiode.

Example 2 In the formula (1), the phthalocyanine derivative of R = n-butyl and Me = copper (II) is easily soluble in chloroform, THF and the like. 1 ml of 3 ml of 100 mg / ml chloroform solution
Platinum is deposited on a glass substrate of 00 cm ² with a thickness of about 0.5 μm by ordinary high frequency sputtering on a substrate, and the solvent is kept for about 3 days while flowing dry nitrogen in an air bag at 20 ° C. I let it evaporate. At this time, place another chloroform container in the air bag, set it to 1/2 of the saturated chloroform vapor pressure at the same temperature for the first half day depending on the amount of chloroform and the nitrogen flow rate, and then set the vapor pressure every 2 hours. It was dropped into 2/3 each, and after about one and a half days, it was placed in an atmosphere of dry nitrogen (flow rate 10 ml / min). After that, vacuum drying is performed for 1 day, film thickness measurement is performed in the same manner as in Example 1,
It was confirmed that a defect-free thin film having an average film thickness of 0.3 μm was formed at about 60 cm ² in the central part of the film, and beryllium (3.5 × 5 mm, thickness 170Å) was vapor-deposited by the same method as in Example 1. Then, electrical measurement and photoelectric measurement were performed. As a result, V _OC 0.77 V, I _SC 0.8 nA / cm ² , rectification ratio 1.7 V 10 ^{3 at} 1 V, diode parameter 1.
45, V _OC 0.74V and I _SC 975nA / as light characteristics
cm ² , ff 0.36, η 4.3 · 10 ^-2 % were obtained.

Example 3 In the formula (1), R = n-hexyl, Me = nickel (I
The phthalocyanine derivative of I) has a melting point of 393 ° C. and 44
It was found by differential scanning calorimeter and thermogravimetric analysis that it had a decomposition point at 6 ° C. 1.0 g of a powder of this substance was placed on an ITO Nesa glass having the same surface area of 100 cm ² as in Example 1 so as to be as uniform as possible, and 400 ± 5 ° C under dry argon.
Heated to melt. After heating to the same temperature for about 5 minutes, IT
The cold CO ₂ gas generated from the dry ice was wiped from the back side of the O plate at a rate of about 500 ml / min, and ₂ times in about 5 minutes.
Quenched to 0 ° C. The film thickness was measured in the same manner as in Example 1,
It was confirmed that a defect-free thin film having an average film thickness of 0.8 μm was formed in about 80 cm ² in the central part of the film, and magnesium was deposited in the same manner as in Example 1 to form a layer of about 150 Å. As in Example 1, but electrical and photoelectric measurements were performed in a dry argon atmosphere. As a result, V _OC 0.92V, I _SC 0.6nA / cm ² , rectification ratio at 1V of 1.93 · 10 ³ as dark characteristics, diode parameter of 1.55,
V _OC 0.88V, I _SC 722nA / cm ² as bright characteristics,
ff of 0.33 and η of 3.1 · 10 ⁻² % were obtained.

Before depositing the M _B to M _{A /} S two-layer structure obtained in Example 4-6 Example 1-3, to form a monomolecular film of arachidic acid cadmium salt by Langmuir-Blodgett method. 2500 cm ² of double-distilled aqueous solution containing 0.5 mmol of cadmium chloride
500 μl of a 1 mg / ml solution of arachidic acid in chloroform was dropped on the surface of and the surface pressure was adjusted to 20 dyn / cm ² by pressing it with a cutting plate. _A two-layer plate of M _A / S is installed vertically on the water surface, and the whole 80 at the speed of 0.5 mm / min.
% Until it was submerged, the monomolecular layer at the air / water interface was removed by vacuum suction, and then pulled up. After this, Example 1
To 3 and was deposited similarly M _B, electrical measurement, light electrical measurements were carried out. As summarized in Table 3, the MIS-type devices obtained in this example are the MSMs of the corresponding examples 1-3.
It can be seen that improvements in V _OC , rectification ratio, diode parameters, and ff are generally recognized as compared with the mold element.

Examples 7 to 14 Arsenic, palladium, tellurium, rhenium, iridium, gold, rhodium having a thickness of about 10 μm were formed on a 2.5 × 5 cm slide glass having a thickness of 1 mm by ordinary high frequency sputtering.
A thin film of ruthenium was formed on each. About 1.0 mg / ml of a chloroform solution of phthalocyanine of R = n-butyl and Me = H ₂ described in Reference Example 15 was added in an amount of 500 μm.
After dropping onto the water interface and evaporating the solvent in the same manner as described in Example 4, the surface pressure was controlled to 20 dyn / cm, and each of the above substrates was vertically dipped 100 times to form an S thin film. After this, Example 1
A thin aluminum layer was formed in the same manner as above to obtain an MSM type element. The characteristics are summarized in Table 4.

Examples 15-34 Prepare 20 sheets of ITO Nesa glass having 2.5 × 5 cm, total thickness of 1 mm, and 10 Ω / sq., And R = n-butyl of Reference Example 16, Me.
= As for the phthalocyanine derivative of copper (II), the same procedure as in Example 7 was performed, but 50 times were accumulated by the horizontal deposition method. Four of them were thermally vapor-deposited with lithium, sodium, potassium and calcium in the same manner as in Example 1. Of the remaining 16 sheets, 8 sheets were each subjected to scandium, titanium, manganese, and
Zirconium, gallium, yttrium, niobium, and cadmium were formed into thin films to obtain MSM type devices. The last 8
The number of sheets is the same as described in Example 4, except that
After a cadmium arachiate monolayer film was formed by the horizontal deposition method, indium, antimony, neodymium, samarium, europium, lutetium, thallium, and lead were each formed into a thin film by high-frequency sputtering to obtain a MIS type device. Their characteristics are summarized in Table 5.

Examples 35 to 47 Thirteen ITO ITO glass was prepared in the same manner as in Example 15, and each of them was formed from 0.5 mg / ml of the chloroform solution of the phthalocyanine derivative of Reference Examples 17 to 29 in 700 μm at the surface pressure shown in Table 6. The obtained monomolecular film was accumulated by the vertical dipping method for the number of times shown in Table 6, and thereafter aluminum was thermally evaporated in the same manner as in Example 1 to obtain an MSM type device. Their properties are summarized in Table 6.

Example 48 It was found by the same measurement as in Example 3 that the phthalocyanine derivative having R = n-tetradecyl and Me = H ₂ of Reference Example 30 had a melting point at 402 ° C and a decomposition point at 456 ° C.
1.0 g of powder of this substance was slowly cooled (about 2 ° C./min) by leaving it as in Example 3 except that it was not rapidly cooled, and returned to room temperature. This film has an average film thickness of 0.83μ in the central area of about 80 cm ^2.
It was found that it had a liquid crystal structure by a polarization microscope. The color tone by visual observation is pale green.
When aluminum was vapor-deposited on this film in the same manner as in Example 1 and a DC voltage of 3 V was applied with the aluminum side being negative and the ITO side being positive, black green was exhibited, and the color tone returned to the original light green by voltage release. It was The response speed of color tone change by voltage application was repeated in about 0.1 seconds, and the color tone recovery by voltage release was repeated in about 0.2 seconds.

Examples 49 to 51 The phthalocyanine derivatives of Reference Examples 31 to 33 were prepared as in Example 7.
In the same manner as above, a cumulative film was formed on three ITO Nesa glass sheets, each having 30 layers at a surface pressure of 20 dyn / cm ² . The film thickness of each phthalocyanine layer is 550, 570, 65.
After confirming 0 Å, aluminum was vapor-deposited in the same manner as in Example 1, and a polarization microscope observation was performed in the same manner as in Example 48 to confirm the liquid crystal structure. Then, voltage application cancellation was repeated in the same manner, and a change in color tone was observed. did. All of them changed from light green to light black green by voltage application, and returned to the original color tone when voltage was released. In all cases, the response speed was 0.03 seconds or less when voltage was applied and 0.08 seconds or less when voltage was released. .

Examples 52 and 53 The phthalocyanine derivative of Reference Example 1 was prepared in the same manner as in Example 7,
However selenium (Examples 52) and germanium (Example 53) in _{M A,} the MSM element using aluminum _{M B,} to give the properties shown in Table 7.

Example 54 Two pieces of disk-shaped glassy carbon having a surface area of 100 cm ² were prepared, and an appropriate amount of 0.3 μm alumina powder and water were placed on a felt, and the disk was pressed while rotating at 1000 rpm for polishing for 3 minutes. After washing with water, in a beaker filled with distilled water,
Use a bath-type ultrasonic cleaner while changing the water 5 times.
Ultrasonic cleaning was performed every 0 minutes. After drying, the polishing surfaces of both disks were placed so as to face each other, and pressed for 10 minutes while rotating in opposite directions at 1000 rpm to obtain a smooth surface. The disk was placed on a rotating device, and 0.8 g of the phthalocyanine derivative powder of Reference Example 32 was placed in the center. Since this phthalocyanine derivative has a melting point at 423 ° C. and a decomposition point at 474 ° C., the temperature of the disc was kept at 430 ° C. in a dry argon atmosphere, and after confirming the melting of the sample, the disc was rotated to 3000 rpm after 1 minute, After maintaining the same temperature and the same number of revolutions for 15 seconds, the rotation was stopped for about 5 minutes, and the temperature was slowly lowered at a rate of 20 ° C./min. After this, after confirming the liquid crystal structure in the same manner as in Example 49, aluminum was vapor-deposited as a counter electrode.
The layer thickness of the phthalocyanine derivative is 0.7 μm, and changes from dark green to dark black green in about 0.5 seconds by applying a voltage,
After releasing the voltage, the original color tone was restored in about 1.5 seconds.

Example 55 A pyrrolitic graphite basal surface having a surface area of 10 cm ² having a freshly cleaved surface was rotated at about 3000 rpm and kept at 430 ° C. under a dry argon atmosphere. 0.1 g of the phthalocyanine derivative of Reference Example 32, which had been heated and melted at 450 ° C. in advance, was added dropwise to the center of the rotating surface, and 1
Turn off the power of rotation after 5 seconds and stop it after about 5 minutes.
The temperature was slowly lowered at a rate of ° C / min. This is followed by Example 52.
The same result was obtained except that the layer thickness was 0.72 μm.

[Brief description of drawings]

The accompanying drawings are drawings schematically showing the existing state of the phthalocyanine derivative used in the present invention at the air / water interface.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI Technical display location H01L 29/91 31/04 H01L 29/91 G 7376-4M 31/04 D

Claims (9)

[Claims] 1. An MSM element formed by laminating a conductive material layer having a large work function, a semiconductor layer and a conductive material layer having a small work function in this order, or a conductive material layer having a large work function, a semiconductor layer, MSM characterized by using a phthalocyanine derivative thin film represented by the following formula (1) as the semiconductor layer in a MIS-type device in which an insulating layer and a conductive material layer having a small work function are laminated in this order.
Or a MIS type element. However, R is a linear or branched hydrocarbon group having 3 to 25 carbon atoms, Me is H ₂ or magnesium or a transition metal ion, and the substitution position of the —OR group is 5 to the isoindoline group of the above formula. Or 6-position. 2. A conductive material having a high work function has a sheet resistance of 30 Ω / sq. The following indium tin oxide, graphite, glassy carbon, arsenic, palladium, tellurium,
MSM or M according to claim (1), characterized in that it is selected from rhenium, iridium, platinum, gold, rhodium, ruthenium, selenium and germanium.
IS type element. 3. A conductive material having a low work function is lithium, beryllium, sodium, magnesium, aluminum, potassium, calcium, scandium, titanium,
The MSM or MIS type device according to claim (1), which is selected from manganese, zirconium, gallium, yttrium, niobium, cadmium, indium, antimony, lanthanides, thallium, and lead. 4. The MIS type device according to claim 1, wherein the insulating layer is composed of a cadmium salt, a mercury salt or an alkaline earth metal salt of a linear saturated fatty acid having 16 to 22 carbon atoms. 5. A semiconductor layer made of a phthalocyanine derivative thin film represented by the following formula (1) is provided on a substrate made of a conductive material having a high work function, and an insulating layer is provided or provided on the semiconductor layer. MSM or MI characterized by forming a conductive material layer having a low work function without
Manufacturing method of S-type element. However, R is a linear or branched hydrocarbon group having 3 to 25 carbon atoms, Me is H ₂ or magnesium or a transition metal ion, and the substitution position of the —OR group is 5 to the isoindoline group of the above formula. Or 6-position. 6. The method according to claim 5, wherein the semiconductor layer is formed by transferring a monomolecular film of a phthalocyanine derivative onto a substrate by a vertical dipping method or a horizontal deposition method. 7. The method according to claim 5, wherein the semiconductor layer is formed by applying a volatile organic solvent solution of a phthalocyanine derivative onto a substrate and evaporating the solvent. 8. The method according to claim 5, wherein the semiconductor layer is formed by melt casting a phthalocyanine derivative on a substrate. 9. The method according to claim 5, wherein the insulating layer is formed by transferring a monomolecular film of a straight-chain fatty acid metal salt onto a substrate by a vertical dipping method or a horizontal deposition method. .