JPH067590B2 - Polymerized phthalocyanine derivative and MSM or MIS type device using the same as a semiconductor layer - Google Patents

Description

The present invention relates to a novel polymerized phthalocyanine derivative, 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. Will be M
The present invention relates to a MIS type element formed by laminating an SM type element, a conductive material layer having a large work function, a semiconductor layer, an insulating layer, and a conductive material layer having a small work function in this order.

[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 elements have been devised. ["Physics of Semiconductor Devices," 2nd Edition, S.
M. Sutse, John Willy and Sun New York (1981) “Physics of Seimconductor Devic
es ”2nd Ed., SM Sze, John Wiluy & Sons, NY
(1981), “Synthetic Metals (Chemical Special Issue 87)” Shirakawa et al., Kagaku Dojin (1980), RC West, NJ Astor, “CRC Handbook of Chemistry and Physics CRC Press, Cleveland (1979), 59th. Edition, E-81: RC West, N.
J. Astel Ed., “CRC Handbook of Cheimstiy and Physi
cs ”CRC Press, Cleaveland (1979), 59th E
d., E-81, M.I. Ozaki et al., Applied Physics Letters: M.M. Ozaki et al., Appl. Phys. Lett 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 created by rotating 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 sneak into the fine pores, and M _A and M _B are directly conducted to function as an element. Easy to lose. Further, when these organic semiconductors are subjected to treatments such as chemical doping and electrochemical doping, for example, poly (acetylene) /
About 10 ² S / cm iodine doped poly (pyrrole) / iodine doped with about 10 2 ^{S /} cm, gives a high conductivity as described, a very low conductivity in the undoped state. Moreover the combination of S layer subjected to doping treatment _M A, and _{M B,} the doping _{agent, M} A / S and _M B / S, proceeds particularly corrosion _M B / S interface, significantly poor stability over time Become. Because it has generally these S layer is used in low conductivity undoped state, remarkably high in the element when the thickness of the S layer resistance 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. Accordingly, the MSM element, prone to impurity level critical S / M _B interface forming a Schottky junction, rectification ratio as a result, the device, intends significantly impair the Dan'odo characteristics. For example, the diode parameter for poly (acetylene) is at most 1.9, and the other values are almost the same, which is far from the ideal state of 1.0. In addition, in the MIS type device, since the I layer needs to be thin enough to expect a tunnel effect (about 20Å),
If the unevenness of the surface of the S layer is severe, the I layer is significantly disturbed, and the characteristics of the element are impaired for the same reason as the above-mentioned MSM type.

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 disadvantage that the reversible 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 (for example, S ．
Baker, Siso Solid Films: S.Baker
Others, such as Thin Solid Films. 99 53 (1983)), the state of the thin film surface is not clear, and in this method, lithium phthalocyanine is hydrolyzed when it contacts the water interface, and as a result, it contains metal. Only a thin film of no phthalocyanine is obtained.

The organic S-layer thin film described above has a drawback that it has poor chemical strength regardless of the manufacturing method. Therefore, when the surface of M _B is coated with vapor deposition, high frequency sputtering, ion beam sputtering or the like to produce an MSM type element or the like, metal atoms having high kinetic energy,
Irregularities easily occur at the S / M _B interface due to collisions of metal ions or metal fine particles, and in the worst case, M _B is embedded in the S layer in the form of atoms or fine particles. As described above, such an interface disorder not only impairs the rectification characteristics and diode characteristics of the element, narrows the range of voltage that can be applied, but also causes irreversible breakdown.

[Object of the Invention]

Therefore, it is an object of the present invention to provide a novel polymerized phthalocyanine derivative having excellent semiconductor properties.
Another object of the present invention is to provide a new MSM or MIS type device that does not have the drawbacks of conventional MSM or MIS type devices.

(Structure of the Invention) The object of the present invention is achieved by a polymerized phthalocyanine derivative obtained by spontaneously polymerizing active species generated by irradiating a vapor of a specific phthalocyanine derivative with a high frequency.

The present invention provides a polymerized phthalocyanine derivative obtained by spontaneously polymerizing active species produced by irradiating the vapor of the phthalocyanine derivative represented by the formula (1) with high frequency, and the derivative has the following formula ( It is presumed to have 2).

However, R represents hydrogen, halogen, or a linear or branched hydrocarbon alkoxy group having 5 or less carbon atoms, and Me represents H ₂ ,
A magnesium or transition metal ion is shown, and the substitution position of R is 5-position or 6-position in the isoindoline group of the above formula.
Rank.

The present invention also provides 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, 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, a thin film of a polymerized phthalocyanine derivative represented by the above-described estimated structural formula (2) is used as the semiconductor layer. A characteristic MSM or MIS type device is provided.

The thin film obtained by introducing active species generated by irradiating the vapor of the phthalocyanine derivative represented by the formula (1) with high frequency to a smooth substrate plane and spontaneously polymerizing the film has a smooth surface and no defects and is extremely strong. Therefore, when forming an MSM or MIS type element by a Schottky junction, a hetero junction, or the like,
It is possible to provide a material system having good rectification characteristics and diode characteristics without any disturbance of the interface in the existing technology or the existing organic semiconductor layer described above. Furthermore, during the polymerization, to course it is no MSM With the M _A to the substrate can be formed MIS type device. Further, for example, for convenience, a polymerized film is formed on a smooth glass surface, peeled off from the surface by an appropriate method such as lift-off, and M _A and M _B are deposited from both sides,
The MSM element is laminated by sputtering or the like, or M _A (or M _B ) is laminated on the glass substrate and peeled off, and then M _B (or M _A ) is laminated on the back surface to form an MSM element. , Etc. become possible. According to this, not only the amount of expensive M _A or M _B used can be reduced, but also an MSM or MIS type device in the form of a laminated thin film having a total thickness of several hundreds μm or less can be produced, and they can be appropriately sized. Any circuit can be designed simply by cutting it and fixing it on a printed circuit board with, for example, a conductive adhesive.

The polymerized phthalocyanine derivative of the present invention is obtained by reacting 4-nitrophthalonitrile represented by the formula (3) with R′—OH (R ′ is a linear or branched alkyl group having 5 or less carbon atoms). -Alkoxyphthalonitrile is obtained and further reacted with ammonia gas using sodium methoxide in dehydrated methanol as a catalyst to give a diiminoisoindoline intermediate (formula (4)) in the presence or absence of a magnesium or transition metal salt. A phthalocyanine derivative (formula (5)) obtained by ring-closing condensation in 2-dimethylaminoethanol in the presence of a solvent under boiling point reflux, or a commercially available phthalocyanine derivative in which R = halogen or hydrogen in formula (1) is reduced under reduced pressure. It is obtained by irradiating steam generated by heating with high frequency to generate active species generated on a smooth substrate and spontaneously polymerizing the active species.

The MSM of the present invention is obtained by using a semiconductive thin film (hereinafter abbreviated as "S") of a polymerized phthalocyanine derivative having a thickness of 20Å to 100 µm thus obtained as a semiconductor layer.
Alternatively, it is a MIS type element.

At this time, the substrate material is indium tin oxide having a sheet resistance of 30 Ω / sq or less, or graphite, glassy carbon, arsenic, palladium, tellurium, rhenium, iridium, platinum, gold, rhodium, ruthenium, selenium,
Conductive material with high work function (M
_A ) is either beryllium on the S layer,
Lithium, sodium, magnesium, aluminum,
Potassium, calcium, scandium, titanium, manganese, zirconium, antimony, lanthanides, thallium, if the coating less conductive work function material selected from lead and (M _B) by conventional thermal vapor deposition or sputtering or the like, the MSM type The device is obtained.

Further, formed between the S and M _B, metal salts of straight-chain saturated fatty acid of 16 to 22 carbon atoms, preferably Kadomiuu salts, monomolecular insulating layer of mercury salts or alkaline earth metal salt (hereinafter I substantially) By doing so, a MIS type element can be obtained. The standard conditions for forming the S layer are phthalocyanine derivatives 1 to 1 of the formula (1).
00 mg, 300-400 ° C., 0.1-1.0 torr, distance from heated phthalocyanine derivative to substrate 1-1
0 cm, high frequency output 1 to 300 W, polymerization time 3 seconds to 5 minutes, and the conditions are determined by the type of phthalocyanine derivative used and the S layer thickness to be formed.

For example, when a thin film having an S layer thickness of about 100 Å is formed on a glass substrate by using R = the above-mentioned phthalocyanine derivative of an alkoxy group, the sample amount is preferably about 30 mg, 350 to
370 ° C., 0.1 to 0.3 Torr, distance 3 to 5 cm, high frequency output, 10 to 30 W, polymerization time 30 seconds to 1 minute, R
= When a thin film having an S layer thickness of about 500Å is formed on a glass substrate using the phthalocyanine derivative of the formula (1) when halogen is used, the sample amount is about 40 mg, 300 to 330 ° C, 0.3 to
0.5 Torr, distance 2 to 4 cm, high frequency output 5 to 15 W, polymerization time 1 to 2 minutes, and glass of a thin film having an S layer thickness of about 100 Å using the phthalocyanine derivative of the formula (1) when R = H. When formed on a substrate, the sample amount is about 30 mg, 330-
350 ° C., 0.5 to 0.7 Torr, distance 4 to 6 cm, high frequency output 30 to 50 W, and polymerization time 30 seconds to 1 minute are suitable.

When the thickness of the S layer thus formed exceeds about 0.1 μm, it can be peeled off from the surface of the smooth substrate by a method such as lift-off. For example, if M _A and M _B (or I / M _B ) are laminated on both sides of the separated S film, it is sufficient for the M _A and M _B layers to be at most 150 Å, so the total thickness is several hundred μm or less. Stacked thin film MSM or MIS
A mold element can be created. Also, on the S layer on the substrate, M _A
(Or to no _{M B} I / _{M B)} was peeled off after forming a thin film, to no _{M B} on the opposite side thereafter I / M
_{A B} (or M _A ) thin film may be formed.

[Effects of the Invention] The polymerized phthalocyanine derivative of the present invention has excellent semiconductor properties, and the MS of the present invention using the same as a semiconductor layer.
The M or MIS type element has excellent rectification characteristics and diode characteristics, and a large current or voltage application of several hundred mA / cm ² ± 10 V
It is not destroyed even in the range of. Therefore, it can be used as a rectifying element such as a diode or a field effect transistor. Further, as shown in the estimated structural formula (2), the semiconductor layer has a phthalocyanine skeleton, exhibits green to blue-green, and has a wide absorption band in the visible region to the near infrared region. Therefore, it can be used as a solar cell. In addition, as described above, a laminated thin film having a total thickness of several hundreds of μm or less can be formed, and the thin film can be cut into any size suitable for the characteristics required at the time of use.

〔Example〕

Next, the present invention will be described in more detail with reference to Examples and Reference Examples.

Reference Example 1 4-Nitro-1,2-phthalonitrile (abbreviated as NPN) 5
0 g (0.29 mol), 11.21 g of methanol (0.
35 mol) was dissolved in 100 ml of dehydrated DMF to give CaC.
l ₂ drying tube equipped with a reflux tube, a nitrogen inlet tube 300ml
The mixture was placed in a 4-necked flask and stirred under a nitrogen atmosphere to give 1,8-diazabicyclo [5,4,0] undecene-.
43.07 ml (0.29 mol) of (7) (abbreviated as DBU) was added and reacted at 60 ° C. for 10 hours. After cooling, concentrate under reduced pressure below 40 ° C, add an appropriate amount of chloroform, and add 600 ml.
Pour into ice-cold 6N HCl and separate the chloroform phase. The aqueous phase is extracted with 100 ml × 3 times of chloroform, combined with the light chloroform phase, dried over anhydrous sodium sulfate, filtered, decolorized with activated carbon, and concentrated under reduced pressure. After cooling, the yellow crystals (unreacted NPN) that had precipitated were removed, and the mother liquor was further concentrated and recrystallized to yield 42.7 g (93.1) of white crystals.
%) Was obtained. As a result of the analysis, the desired 4-methoxy-1,2-
Found to be phthalonitrile.

4-methoxy-1,2-phthalonitrile NMR (CDCl ₃ , δppm): Ha7.1, 7.2
(1H), Hb7.2 (1H), Hc7.65, 7.7
(1H), CH ₃ 3.9 (3H) IR (KBr tablet, cm
^-1 ): ν _φH 3100, 3050, 3000, 2950, 2850, νC≡N2250, ν _ring 161
0 The whole amount of this was put in the same apparatus as described above, 2 g of sodium methoxide was added to 200 ml of dehydrated methanol, and the reaction was carried out at room temperature for 2 hours while vigorously passing dry ammonia gas, and for 1 hour under boiling point reflux. The white precipitate formed after cooling was collected by filtration and dried in vacuum to obtain 43.1 g (91.1%) of 5-methoxydiiminoisoindoline. This product has a strong hygroscopic property, and IR (KBr tablets, cm ^-1 ) gives ν _NH 340.
The structure was confirmed by the appearance of 0, δ _NH 1640 and the disappearance of ν _{C = N} 2250.

Reference Examples 2 to 7 The same apparatus as in Reference Example 1 was used to carry out the reaction described in Table 1 to obtain the corresponding 4-alkoxy-1,2-phthalonitrile. However, those having 4 or more carbons are oily, and instead of recrystallization, a φ10 × 30 cm silica gel column (100 to 200 mesh) was used, chloroform was used as a developing solvent, and the main outflow of the Rf value shown in Table 1 was used. Part was collected and the solvent was distilled off under reduced pressure.

Reference Examples 8 to 13 All the 4-alkoxyphthalonitriles obtained in Reference Examples 2 to 7 were treated in exactly the same manner as in the latter stage of Reference Example 1, and the structure was similarly confirmed by IR. Diiminoisoindoline 49.2 g (96.3%), 5-
(N-propoxy) diiminoisoindoline 51.8 g
(96.2%), 5- (n-butoxy) diiminoisoindoline 57.6 g (96.4%), 5- (tert-butoxy) diiminoisoindoline 59.8 g (98.2)
%), 5- (n-pentoxy) diiminoisoindoline 59.0 g (98.1%), and 5- (1-methylbutoxy) diiminoisoindoline 60.1 g (97.4).

Reference Example 14 5-methoxydiiminoisoindoline of Reference Example 1 17.
5 g (0.1 mol) is dispersed in 50 ml of dehydrated 2-dimethylaminoethanol, and boiling point is refluxed for 5 hours while stirring in a 200 ml Erlenmeyer flask equipped with a reflux tube with a CaCl ₂ drying tube. The content was thrown into 1 warm methanol with stirring, and the green precipitate formed was collected by filtration and dried to obtain 12.1 g (76.3%) of a phthalocyanine derivative of R = methoxy and Me = H _{2 in} the formula (1). Got It is insoluble in almost all organic solvents except that it dissolves in chloroform at about 10 ^-5 mol / about.

Elemental analysis (wt%, calculated value in parentheses): C68.15 (68.13), H4.17 (4.1)
3), N17.70 (17.66) visible absorption spectrum (chloroform, nm, parenthesized lo)
g ε): 702 (4.96), 664 (4.88),
642 (4.53), 605.5 (4.30) Reference Examples 15 to 20 Similar to Reference Example 14, except that 5-alkoxydiiminoisoindoline shown in Table 2 was used and R = shown in Table 2 was used. A phthalocyanine derivative of alkoxy, Me = H ₂ , was obtained.

Reference Example 21 Similar to Reference Example 14, except that 14.9 g of cuprous chloride (0.
(15 mol) to carry out the reaction, throw the crude product in 20% hydrochloric acid-methanol 1, collect the resulting precipitate by filtration, repeat washing with methanol, and dry under reduced pressure to obtain R = methoxy in the formula (1), 12.3 g (70.7%) of Me = copper (II) phthalocyanine derivative was obtained.

Elemental analysis (wt%, calculated value in parentheses): C62.07 (62.11), H3.44 (3.4)
7), N16.16 (16.10) visible absorption spectrum (chloroform, nm, parenthesized lo)
g ε): 680 (5.04), 615 (4.60),
567 ^sh , 381 (4.40) Reference Examples 22 to 27 In the same manner as in Reference Example 21, except that the charges shown in Table 3 were reacted and treated in the same manner, corresponding tetraalkoxy metal phthalocyanine derivatives were obtained. However, when Me = magnesium (II) and zinc (II), the reprecipitation operation was performed using warm methanol instead of acidic methanol.

As described above, 4-nitro-1,2-phthalonitrile was used as a starting material to react with alcohol in the presence of a base catalyst to obtain 4-alkoxy-1,2-phthalonitrile, and further reacted with ammonia gas to give 5 The corresponding tetraalkoxy (metal) phthalocyanine derivative is obtained by carrying out the cyclization reaction in the absence or presence of a metal salt via an alkoxydiiminoisoindoline intermediate. Although metal chlorides were used in this reference example, generally, a counter anion having no oxidizing power (for example, ClO ₄ ⁻ , ClO ₃ , Cl) is used.
^{_{O -, NO 3 -, ▲}} SO 2- 4 ▼ it may be a metal salt of an excluded) such as, for example, acetates are preferred, and coordination of the results acetylacetonato complexes total charge number becomes 0 Are also preferable.

Example 1 10 mg of tetramethoxyphthalocyanine of Reference Example 14 was placed in the 6th part of the apparatus shown in the attached drawing, and a commercially available ITO Nesa glass (2.5 × 5 cm, thickness 1.5 mm, in the figure) was used as a substrate for forming a semiconductor layer. Then, it is indicated by 3) and 2 cm (2 'directly above 6)
2.5 cm above), 2 is located 4.5 cm from 2 ', and 4 is located between 3 and 6. The gas was exhausted from the exhaust pipe indicated by 7 to 10 ^-3 torr, the exhaust was temporarily stopped, and the argon gas was injected from the intake pipe indicated by 8. After repeating this evacuation-injection of argon gas three times, the temperature was maintained at 10 ^-1 torr, and a current was passed through 6 to maintain the temperature at 300 ° C. After confirming that tetramethoxyphthalocyanine has begun to adhere to the surface of the shutter plate indicated by 4, the electric current is applied to generate a high frequency of 10W 13.56MHz between 2-2 ', and the shutter is released for about 5 seconds. Move the plate to the side from the middle position between 3 and 6,
The active species generated by applying a high frequency to the vapor of the sample were made to directly collide with the substrate of 3. After maintaining this state for 20 seconds, the shutter was closed and the power supply for high frequency and heating was immediately cut off and the mixture was allowed to cool. Argon was injected into the device to return it to normal pressure, the substrate was taken out and placed in a thermal evaporation device, and aluminum was slit on the substrate in the usual manner into a slit shape of about 3.5 × 5 mm,
It was vapor-deposited to a thickness of 150Å. After that, a part of the semiconductor thin layer was scraped off for elemental analysis, and lead wires were installed on the exposed portion of the ITO surface and the aluminum vapor deposition portion to form an MSM type element and connected to a DC conductivity measuring device. The voltage was swept at a rate of 2 mV / sec in the dark or under the irradiation of white light, the voltage-current characteristics were examined from the current value at that time, various parameters were determined, and the characteristics of the MSM type element were evaluated. Further, visible absorption spectrum measurement was performed on a portion where aluminum was not vapor-deposited. Further, the semiconductor layer thickness was determined by a stylus type surface roughness meter.

Elemental analysis of semiconductor layer (wt%): C72, 16, H3.
43, N20.10 Reference 1 Theoretical value of phthalocyanine: C74.99, H3.15, N21.86 Reference 2 Theoretical value of tetramethoxyphthalocyanine C68.35, H3.82, N17.71 Visible absorption spectrum (nm): 700 , 665, 64
0,602,555 Reference phthalocyanine spectrum: 698,665,
638, 602, 554 Device characteristics Dark: Rectification ratio 1.42 · 10 ³ (However, 1V
In the following; the same applies hereinafter), diode parameter 1.6
Open circuit voltage 0.75 V, closed current 0.25nA / cm ² Akirashita: open-circuit voltage 0.70 V, closed current 850nA / c
m ² , fill factor 0.32, photoelectric conversion efficiency 2.8
10 ^-2 % Semiconductor layer thickness: 220Å This semiconductor layer is insoluble in all organic solvents, concentrated sulfuric acid, etc. (The starting material tetramethoxyphthalocyanine is slightly soluble in chloroform, hot chloronaphthalene, soluble in concentrated sulfuric acid) , Its visible absorption spectrum shows that the phthalocyanine skeleton is maintained, but it is an intermediate spectrum between phthalocyanine and tetramethoxyphthalocyanine, and elemental analysis shows that 2.5 of 4 methoxy groups have been lost. , It is considered that the phthalocyanine skeleton has a structure similar to the putative structural formula (2) in which phthalocyanine skeletons are polymerized by bonding with each other at the site where the methoxy group is lost. Further to the semiconductor layer and S, ITO to M _A, MSM element using aluminum to M _B exhibited good characteristics as described above, the rectifying element, a diode, can be utilized in the photodiode or the like was found. Further, this element is not destroyed even by applying a voltage within the range of ± 10V.

Example 2 As in Example 1, but using 30 mg of phthalocyanine,
Rather than direct heating from the boat, the temperature of the sample was 340 ° C., the degree of vacuum was 0.6 Torr, the distance between 3 and 6 was 5 cm, and the distance between 2 and 2 ′ was 10 by using the heater shown in FIG.
cm, high frequency output 40W, 2.5 × 2.5cm thickness 1
A semiconductor layer corresponding to a platinum plate of mm was formed for 40 seconds.
After this, an MSM element was prepared in the same manner as in Example 1, and elemental analysis, spectrum measurement, characteristic measurement, and film thickness measurement were performed.

Elemental analysis of semiconductor layer (wt%): C75.44, H2.
57, N21.99 visible absorption spectrum (nm): 699, 665, 63
8,602 Element characteristics Dark: Rectification ratio 1.62 · 10 ³ , diode parameter 1.55 Open voltage 0.76V, closed current 0.92nA / cm ² Bright: Open voltage 0.71V, closed current 910nA / c
m ² , fill factor 0.33, photoelectric conversion efficiency 3.4
10 ^-2 % Semiconductor layer thickness: 100Å This semiconductor layer is insoluble in all organic solvents, concentrated sulfuric acid, etc., and corresponds to polymerized phthalocyanine which is bonded by losing 3 hydrogen atoms in the benzene nucleus of phthalocyanine by spectrum and elemental analysis. Further, while the phthalocyanine thin film formed by general vapor deposition has a fragile shape that can be scraped off just by touching it, this semiconductor layer has excellent mechanical strength such that it is not easily scratched unless it has a sharp cutting edge. Further, as shown in the element characteristics, it can be seen that it can be used as a rectifying element, a diode, a photodiode and the like.

In the same manner as in Example 3 to 23 Example 1, except to create a semiconductor layer under the conditions summarized in Table 4, the MSM element by depositing a M _B, to give the results shown in Table 5. Further, on each semiconductor layer shown in Table 4, as the air / water interface to form a single layer film of straight-chain saturated fatty acids created, MIS type device further deposited to a high frequency sputtering M _B 6 The results shown in the table were obtained.

In the table, V _OC : I _SC , R. R. , D. P. ,
η indicates an open circuit voltage, a closed circuit current, a current ratio, a diode parameter, a fill factor, and a photoelectric conversion efficiency.
From the elemental analysis and the visible absorption spectrum, the structure of the semiconductor layer has three R groups (Examples 3 to 5, 7 to 11, and 14 to 1).
6) to 2.5 (6, 12, 13) to 3.5 (17) are lost, and the structure seems to be similar to the formula (2) polymerized at the site.

Example 24 Cobalt (II) tetra (tert-butoxy) of Reference Example 25
150 mg of phthalocyanine were polymerized as in Example 1, but for 5 minutes. Polyvinyl alcohol was spread thickly (about 1/10 mm) from a concentrated aqueous solution on a paper with a smooth surface, and was adhered onto the semiconductor layer that was made aside. After drying
The semiconductor layer was peeled off, poured into water to dissolve polyvinyl alcohol, the semiconductor layer was separated from the paper surface, and sufficiently washed in water. After performing the measurement of the surface roughness meter and visible absorption spectrum, by high frequency sputtering platinum on one side,
A thin film of aluminum was formed on the opposite surface by thermal evaporation to form a three-layer structure MSM type element, and its electrical characteristics were measured to obtain the following results.

Elemental analysis of semiconductor layer (wt%): C67.37, H3.
44, N17.52, Co9.24 Reference (theoretical value of starting complex): C67.20, H5.4
0, N13.06, Co6.87 Visible absorption spectrum (nm): 675, 650 ^sh 610 Reference (theoretical value of starting complex): 673: 645 ^sh , 61
0 Element characteristics Dark: Rectification ratio 1.75 · 10 ³ , Diode parameter 1.6 Open voltage 0.77 V, Closing current 0.7
7 nA / cm ² light: Open voltage 0.71 V, closed circuit current 865 nA / c
m ² , fill factor 0.34, photoelectric conversion efficiency 3.2
10 ^-2 % Layer thickness: M _A (Pt) 570Å S 0.4 μm M _B (Al) 150 Å In addition, from the elemental analysis and spectrum measurement, the structure of this semiconductor layer was found to have lost 3 R and was polymerized at that site. Formula (2)
It seems that the structure is similar to. This element has a total thickness of about 0.5
It is in the form of a thin film of μm and can be cut into any area for use.

Example 25 200 mg of ruthenium (II) tetra (1-methylbutoxy) phthalocyanine of Reference Example 27 was polymerized exactly as in Example 1, but for 7 minutes. After further surface coating of platinum in the usual high-frequency sputtering, the S + M _A layer in the same manner as in Example 24 was peeled from the glass substrate. The S + M _A layer in the same manner as in Example 24 apart from the paper surface, taking transferred from the air / water interface of the single layer film of arachidic acid cadmium salt 20 dyn / cm by vertical dipping method, MIS type device further thermally depositing aluminum The following results were obtained.

Elemental analysis of semiconductor layer (wt%): C63.74, H3.
52, N16.01, Ru14.55 Reference (theoretical value of starting complex): C65.32, H5.6
9, N 11.72, Ru10.57 Visible absorption spectrum (nm): 692, 661 ^sh 620 Reference (absorption band of starting complex): 689, 658 ^sh , 61
7 Device characteristics Dark: Rectification ratio 1.88 · 10 ³ , diode parameter 1.5 open circuit voltage 0.81 V, closed circuit current 0.
75 nA / cm ² light: Open voltage 0.77 V, closed circuit current 920 nA / c
m ² , fill factor 0.36, photoelectric conversion efficiency 3.8
10 ^-2 % Layer thickness: M _A (Pt) 750Å S 1.2 μm M _B (Al) 140 Å In addition, from the elemental analysis and visible absorption spectrum measurement, the structure of this semiconductor layer lost three R groups, A structure similar to that of formula (2) polymerized by

Example 26 Similar to Example 24, except that cobalt (II) tetra (tert
- using butoxy) phthalocyanine 500mg, by 20 minutes polymerization, selenium as _{M A,} was MSM type element Aluminum was thermally evaporated as _{M B.}

Elemental analysis of semiconductor layer (wt%): C67.40, H3.
42, N17.55, Co9.21 Visible absorption spectrum (nm): 675, 650 ^sh 610 Device characteristics Dark: Rectification ratio 1.8 · 10 ³ , Diode parameter 1.5 Open circuit voltage 0.79 V, Closed circuit current 0.5
² nA / cm ² light: Open voltage 0.72 V, circuit current 760 nA / c
m ² , fill factor 0.36, photoelectric conversion efficiency 3.1
^10-2% layer _thickness: the other using a germanium M A (Se) 250Å S 76μm M B (Al) 150Å Example 27 _{M A} in the same manner as in Example 26 to create the MSM element.

Elemental analysis of semiconductor layer (wt%): C67.42, H3.
44, N17.52, Co9.18 Visible absorption spectrum (nm): 675, 650 ^sh 610 Device characteristics Dark: Rectification ratio 1.9.10 ³ , Diode parameter 1.5 Open circuit voltage 0.77V, Closed circuit current 0.4
² nA / cm ² light: Open voltage 0.71 V, circuit current 740 nA / c
m ² , fill factor 0.36, photoelectric conversion efficiency 3.0
^10-2% layer _{thickness: M A (Ge) 220Å S} 82μm M B (Al) 160Å

[Brief description of drawings]

The accompanying drawings are schematic side sectional views showing an example of an apparatus for producing a semiconductor layer composed of a thin film of a polymerized phthalocyanine derivative of the present invention. (Explanation of figure number) 1 ・ ・ ・ Bell jar (made of thick glass) of about 25φ × 30cm, 2 and 2 '・ ・ ・ High-frequency generating electrode plate and its counter electrode plate (disc-shaped φ10 × 0.3cm) 3 ... Substrate on which semiconductor layer is formed 4 ... Shutter (φ10 ×
0.3 cm), 5 ... Tungsten heater (6 in the figure)
Although it is written right above, it is actually installed about 0.5 cm diagonally above 6 at an angle of 60 ° from the vertical. ), 6 ...
・ Tungsten or tantalum boat (with sample placed inside and 0.5 cm above the center line of 2'which also functions as a heater), 7 ... an exhaust pipe connected to a vacuum system, 8 ... Intake pipe connected to an argon cylinder, 9 ... Teflon rubber O-ring, 10 ... Board, 11 ... 2 and lead wires for supplying power to 2'5 and 6.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location H01L 29/784 31/04

Claims (9)

[Claims] 1. A polymerized phthalocyanine derivative obtained by spontaneously polymerizing active species produced by irradiating a vapor of a phthalocyanine derivative represented by the following formula (1) with high frequency. However, R represents hydrogen, halogen, or an alkoxy group of a true chain or branched hydrocarbon having 5 or less carbon atoms, Me represents H ₂ ,
A magnesium or transition metal ion is shown, and the substitution position of R is 5-position or 6-position in the isoindoline group of the above formula.
Rank. 2. 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, In a MIS-type device in which an insulating layer and a conductive material layer having a small work function are stacked in this order, an active species generated by irradiating a vapor of a phthalocyanine derivative represented by the formula (1) with high frequency is used as the semiconductor layer. MSM or MIS characterized by using a thin film of a polymerized phthalocyanine derivative obtained by natural polymerization
Mold element. However, R represents hydrogen, halogen, or a linear or branched hydrocarbon alkoxy group having 5 or less carbon atoms, and Me represents H ₂ ,
R represents a magnesium or transition metal ion, and the substitution position of R is 5-position or 6-position in the isoindoline group of the above formula.
Rank. 3. A polymerized phthalocyanine derivative thin film having the formula:
The phthalocyanine derivative of (1) is heated and vaporized under reduced pressure,
The MSM or MIS type element according to claim (2), which is obtained by spontaneously polymerizing active species generated by irradiating the vapor with a high frequency. 4. A conductive material having a high work function has a sheet resistance of 30 Ω / sq. The following isodium tin oxide, graphite, glassy carbon, arsenic, palladium, tellurium,
MSM or M according to claim (2), characterized in that it is selected from rhenium, iridium, platinum, gold, rhodium, ruthenium, selenium and germanium.
IS type element. 5. A conductive material having a low work function is lithium, beryllium, sodium, magnesium, aluminum, potassium, calcium, scandium, titanium,
Manganese, zirconium, antimony, lanthanides,
The MSM or MIS type element according to claim (2), which is selected from thallium and lead. 6. The M according to claim 2, wherein the insulating layer comprises a metal salt of a linear saturated fatty acid having 16 to 22 carbon atoms.
IS type element. 7. The MIS type element according to claim (2), wherein the metal salt is a cadmium salt, a mercury salt or an alkaline earth metal salt. 8. An insulating layer made of a straight-chain fatty acid metal salt is formed by forming a monomolecular film on an air / water interface and transferring it onto a semiconductor layer by a vertical dipping method or a horizontal adhesion method. The MIS type element according to claim (2), which is characterized by being present. 9. The MSM or MIS type device according to any one of claims (2) to (8), wherein the semiconductor layer has a thickness of 20Å to 100 μm.