JPH08851B2 - Phthalocyanine derivative polymerized containing a doping agent and MSM or MIS type device having the same as a semiconductor layer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application] The present invention provides a novel polymerized phthalocyanine derivative thin film, 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. The present invention relates to an MIS type element formed by laminating a stacked MSM 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]

An organic semiconductor (S) such as poly (acetylene), poly (diacetylene), poly (pyrrole), poly (thienylene), etc., between a metal having a high work function (M _A ) and a metal having a low work function (M _B ). Many devices of MSM type sandwiching thin layers, or MIS type devices in which a thin layer of an insulator (I) is further incorporated between S and M _B have been devised. ["Fixics
Of Semiconductor Devices "2nd Edition, SM Suze, John Willy & Sun, New York (1981)" Physics of Seimconductor Devices "2nd E
d., SMSze, John Wiley & 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: RCWest, NJ
Astle Ed., “CRC Handbook of Cheimstry and Physics”
CRC Press, Cleaveland (1979), 59th Ed., E-81, M. Ozaki and others, Applied Physics Letters: M. Ozaki
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 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 will dig into the fine pores and become M _A.
It is easy for M _B to directly conduct and lose its function as an element. In addition, when these organic semiconductors are subjected to treatments such as chemical doping and electrochemical doping, for example, poly (acetylene) / iodine-doped approximately 10 ² S / cm, poly (pyrrole) /
It has a high conductivity of about 10 ² S / cm when doped with iodine, but has a very low conductivity in the undoped state. Moreover, if the doped S layer is combined with M _A and M _B , the doping agent causes corrosion at M _A , / S and M _B / S, especially at the M _B / S interface, resulting in remarkable stability over time. Get scarce. Therefore, these S layers are generally used in a dedoped state with low electrical conductivity, but in order to prevent the above-mentioned penetration of M _B particles, S layers are used.
If the layer is thickened, the resistance inside the element becomes extremely high, and it is impossible to pass a current sufficient for practical use. 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 diode characteristics. For example, the diode parameter for poly (acetylene) is at most 1.9, and other values are almost the same, which is far from the ideal state of 1.0. In the MIS type element,
Since it is necessary to reduce the thickness of the I layer to the extent that a tunnel effect can be expected (about 20Å), if the irregularities on the surface of the S layer are severe, the I layer will be significantly disturbed, and for the same reason as the MSM type described above, the device characteristics will be Be damaged.

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 etc., 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 .Baker et al., Thin Solid Films: S.Baker et al.
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, resulting in metal-free phthalocyanine. Only a thin film of is obtained.

The organic S-layer thin film described above has a drawback that it has poor chemical strength regardless of the manufacturing method. Thus, deposition of M _B on its surface, when the high-frequency sputtering, by coating with an ion beam sputtering or the like to create a MSM type device or the like, a high metal atom having kinetic energy, S / M _B due to the collision of the metal ions or metal particles Concavities and convexities are likely to occur at the interface, and in the extreme 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, an object of the present invention is to provide a novel polymerized phthalocyanine derivative thin film 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) An object of the present invention is to obtain a polymerization product containing a doping agent, which is obtained by spontaneously polymerizing an active species generated by irradiating a mixed vapor of a specific phthalocyanine derivative and a specific doping agent with a high frequency. Phthalocyanine derivative thin film.

The present invention relates to a phthalocyanine derivative represented by the formula (1) and iodine, SO ₃ , AsF ₅ , BF ₃ , SbF ₅ , NbF ₅ , TaF ₅ , and PF _5.
The present invention provides a polymerized phthalocyanine derivative thin film containing a doping agent, which is obtained by irradiating a mixed vapor of a doping agent selected from the above with high frequency, and the derivative has the following formula (2): It is estimated to be.

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

However Is a phthalocyanine group excluding R in the formula (1), Z is the above-mentioned doping agent, and x and y are percentages representing the existing ratios of the phthalocyanine group and Z, respectively, x + y = 100, y
≦ 50.

The present invention is also a conductive material layer having a large work function, a semiconductor layer and an MSM element formed by laminating 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 stacking an insulating layer and a conductive material layer having a small work function in this order, a phthalocyanine polymerized as a semiconductor layer containing a doping agent represented by the estimated structural formula (2). MSM or M characterized by using a thin film of derivative
It is intended to provide an IS type element.

A thin film obtained by introducing active species generated by irradiating a mixed vapor of the phthalocyanine derivative represented by the formula (1) and the above-mentioned doping agent with a high frequency to a smooth substrate plane and spontaneously polymerizing the film has a smooth surface and defects. There is no and is extremely strong.
Therefore, when forming an MSM or MIS type element by a Schottky junction heterojunction or the like, a material system having good current characteristics and diode characteristics without existing interface technologies in existing technologies or existing organic semiconductor layers described above. Can be given. In addition, when M _A is used for the substrate during polymerization, it is of course possible to directly form an MSM or MIS type element. For example, for convenience, a polymer film is formed on a smooth glass surface,
Peel off from the surface by a suitable method such as lift-off and from both sides
M _A and M _B are laminated by vapor deposition, sputtering, etc. to form an MSM element, or M _A (or M _B ) is laminated on the glass substrate and peeled off, and then M _B (or M _A ) is placed on the back surface. It is possible to use a method such as stacking on the above to form an MSM element. According to this, not only the amount of expensive M _A or M _B used can be reduced, but also a laminated thin film MSM or MIS type element having an overall thickness of several hundred 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.

Furthermore, in the case of an organic compound semiconductor, when a suitable Lewis acid is allowed to coexist as a doping agent, the conductivity is higher and the p-type semiconductor is excellent.
(Doping and MSM of these doped organic semiconductors, M
Regarding the IS type element, for example, “Fizick of Semiconductor Device, 2nd Edition: SM Zutse, John Willie and Sons, New York: Physics o
f Semiconductor Devices 2nd Ed., "SMSze, John Wile
y & Sons, NY (1981); “Synthetic metals (Chemical special edition 87)”, Shirakawa et al., Kagaku Dojin (1980)). However, these doping agents are the during normal organic semiconductor, or so can be further diffused I layer, characteristics of the device to corrode M _B reaches the M _B interface is cracked significantly damaged. In particular, it has very poor stability over time. However, the semiconductor layer of the present invention has the doping agent firmly embedded therein, and the diffusion thereof does not occur, so that the above-mentioned deterioration does not occur, and the advantage of the doping, that is, the improvement in conductivity and the P-type characteristic, is achieved. There are features that are expected to improve.

The polymerized phthalocyanine derivative thin film containing the doping agent according to the present invention is represented by the formula (3): 4-nitrophthalonitrile and R'-OH (R 'is a linear or branched alkyl group having 5 or less carbon atoms. Group) to obtain the corresponding 4-alkoxyphthalonitrile, and further reacts with ammonia gas using sodium methoxide in dehydrated methanol as a catalyst to give magnesium or transition via diiminoisoindoline intermediate (formula (4)). Phthalocyanine derivative (formula (5)) obtained by ring-closing condensation in 2-dimethylaminoethanol under boiling point reflux in the presence or absence of a metal salt, or R = halogen or hydrogen in formula (1) commercially available the phthalocyanine derivative, and steam generated by heating under reduced pressure, _{iodine, SO 3, AsF 5, BF} 3, SbF 5, NbF 5, TaF 5, PF 5 Leads to active species generated by irradiating a high frequency in a mixed vapor of doping agent chosen on a smooth substrate obtained by spontaneous polymerization.

The MSM of the present invention is obtained by using a semiconductive thin film (hereinafter abbreviated as "S") of a phthalocyanine derivative polymerized with a doping agent 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,
When either of the larger conductive material work function, such as germanium (M _A) are beryllium on the S layer, aluminum, scandium, titanium, manganese,
Zirconium, antimony, lanthanides, thallium,
An MSM type element can be obtained by coating a conductive material (M _B ) selected from lead having a small work function by ordinary thermal evaporation or stuttering.

Further, formed between the S and M _B, metal salts of straight-chain saturated fatty acid of 16 to 22 carbon atoms, preferably a cadmium salt, a monomolecular insulating layer of mercury salts or alkaline earth metal salt (hereinafter I substantially) If this is done, a MIS type element can be obtained. The standard condition for forming the S layer is 1 to 500 mg of the phthalocyanine derivative of the formula (1).
And a mixture of the above-mentioned doping agent in an equimolar amount to 1/10 molar amount thereof, 300 to 400 ° C., 1 to 3 torr, distance from heated mixture to substrate 1 to 5 cm, high frequency output 1 to 100
W, polymerization time is 3 seconds to 7 minutes, and the conditions are determined by the type of phthalocyanine derivative used, the type of doping agent, the S layer thickness to be formed, and x and y to be set. For example, R = phthalocyanine derivative of an alkoxy group as described above, using the doping agent iodine, the S layer thickness of about
When forming a thin film of 100Å, x = 60%, y = 40% on a glass substrate, the sample amount is about 30 mg + equimolar amount of iodine, 300
To 350 ° C., 2 torr, the distance 2-3 cm, high frequency output 10～30W, polymerization is the time 30 seconds to 1 minute, S thickness of about 500Å using a phthalocyanine derivative and AsF ₅ in the case of R = H, x = 80 %, Y
= 20% of the thin film to an equimolar mixture of phthalocyanine derivatives + AsF ₅ when formed on a glass substrate 100 mg, 300 to 32
0 ℃, 0.9-1.5torr, distance 2-4cm, high frequency output 5-15
W, polymerization time of 1 to 2 minutes is suitable, and R = halogen phthalocyanine derivative and SO ₃ are used to form S layer thickness of about 200Å, x
= 90%, y = 10% thin film on a glass substrate, a phthalocyanine derivative + SO ₃ 3/1 molar ratio mixture 70 mg
The suitable temperature is 320 to 340 ° C., 1.5 to 3 torr, distance 3 to 4 cm, high frequency output 30 to 50 W, and polymerization time 30 seconds to 1 minute.

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, on both sides of the peeled S layer,
If M _A and M _B (or I / M _B ) are laminated, it is sufficient for the M _A and M _B layers to be at most 150 Å. Therefore, the total thickness of the laminated thin-film MSM or MIS type is several hundred μm or less. Elements can be created.
Also, M _A (or M _B or I / M _B ) on the S layer on the substrate
After forming a thin film, peel it off, and then on the opposite surface
An M _B or I / M _B (or M _A ) thin film may be formed.

〔The invention's effect〕

The phthalocyanine derivative thin film polymerized containing the doping agent of the present invention has excellent semiconductor characteristics, and the MSM or MIS type element of the present invention using this as a semiconductor layer has excellent rectification characteristics and diode characteristics, It is not destroyed even in the range of large current or voltage of ± 10V of several hundred mA / cm ² or more. Therefore, it can be used as a rectifying element such as a diode or a field effect transistor. In addition, as shown in the estimated structural formula (2), the semiconductor layer has a phthalocyanine bone nucleus,
It has a blue-green color and has a wide absorption band in the visible to 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) 50g
(0.29 mol), 11.21 g of methanol (0.35 mol) in 100 ml
Dissolved in dehydrated DMF, put into a 300 ml 4-necked flask equipped with a reflux tube with CaCl ₂ drying tube and a nitrogen introduction tube, and stirred under nitrogen atmosphere under 1,8-diazabicyclo [5,4,0] undecene- ( 7) Add 43.07ml (0.29mol) of (abbreviated as DBU), 60 ℃
Was reacted for 10 hours. After cooling, concentrate under reduced pressure at 40 ° C or lower, add an appropriate amount of chloroform and pour into 600 ml of ice-cooled 6N-HCl to separate the chloroform phase. 100 ml of water phase x 3
Extracted with chloroform twice, combined with the chloroform phase, dried over anhydrous sodium sulfate, filtered, decolorized with activated carbon,
Concentrate under reduced pressure. Yellow crystals that precipitate after cooling (unreacted NP
N) was removed, and the mother liquor was further concentrated and recrystallized to obtain 42.7 g (93.1%) of white crystals. As a result of the analysis,
It was found to be methoxy 1,2-phthalonitrile.

4-methoxy-1,2-phthalonitrile NMR (CDCl ₃ , δppm): Ha7.1, 7.2 (1H), Hb7.2 (1H),
Hc 7.65, 7.7 (1H), CH ₃ 3.9 (3H) IR (KBr tablets, c
m ^-1 ): νφ _H 3100, 3050, 3000, ν _CH3 2950, 2850, ν
_{C ≡ N} 2250, νring 1610 Put the whole amount in the same device as above, add 2 g of sodium methoxide in 200 ml of dehydrated methanol, and let dry ammonia gas vigorously pass through it for 2 hours at room temperature and for 1 hour under boiling point reflux. It was made to react. The white precipitate formed after cooling was collected by filtration and dried in vacuum to obtain 53.1 g (91.1%) of 5-methoxydiiminoisoindoline. This material is a strong hygroscopic, IR (KBr tablet, cm ^-1) than [nu _NH 3400, confirmed the structure by the disappearance of the appearance and ν _{C ≡ N} 2250 of [delta] _NH 1640.

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 with 4 or more carbons are oily, and instead of recrystallization, a silica gel column (10 x 30 cm) (10
(0 to 200 mesh), chloroform was used as a developing solvent, the main outflow portion of Rf value shown in Table 1 was fractionated, 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 (9
6.4%), 5- (tert-butoxy) diiminoisoindoline 59.8 g (98.2%), 5- (n-pentoxy) diiminoisoindoline 59.0 g (98.1%), 5- (1-methylbutoxy) diimino 60.1 g (97.4) of isoindoline was obtained.

Reference Example 14 5-methoxydiiminoisoindoline 17.5 of Reference Example 1
g (0.1 mol) is dispersed in 50 ml of dehydrated 2-dimethylaminoethanol, and the mixture is refluxed at boiling point for 5 hours while stirring in a 200 ml Erlenmeyer flask equipped with a reflux tube with a CaCl ₂ drying tube. Content 1
The resulting green precipitate 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). It is insoluble in almost all organic solvents except that it dissolves in chloroform at about 10 ^-5 mol / l.

Elemental analysis (wt%, calculated value in parentheses): C68.15 (68.13),
H4.17 (4.13), N17.70 (17.66) Visible absorption spectrum (chloroform, nm, parenthesized log
ε): 702 (4.96), 664 (4.88), 642 (4.53), 605.
5 (4.30) Reference Examples 15 to 20 In the same manner as in Reference Example 14, but using 5-alkoxydiiminoisoindoline shown in Table ₂ , phthalocyanine derivatives of R = alkoxy and Me = H ₂ shown in Table ₂ were obtained. It was

Reference Example 21 In the same manner as in Reference Example 14, except that 14.9 g (0.15 mol) of cuprous chloride was added and the reaction was carried out, the crude product was thrown into 20% hydrochloric acid-methanol 1, and the resulting precipitate was collected by filtration and methanol was added. The washing was repeated and dried under reduced pressure to obtain 12.3 g (7%) of the phthalocyanine derivative of R = methoxy and Me = copper (II) in the formula (1).
0.7%) was obtained.

Elemental analysis (wt%, calculated value in parentheses): C62.07 (62.11),
H3.44 (3.47), N16.16 (16.10) Visible absorption spectrum (chloroform, nm, log in parentheses)
ε): 680 (5.04), 615 (4.60), 567sh, 381 (4.4
0) 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, Me = magnesium (I
In the case of I) and zinc (II), warm methanol was used instead of acidic methanol for reprecipitation.

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, which was 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 this reference example using metal chlorides, generally no oxidizing power counter anion (e.g. ^{_{ClO 4 -, ClO 3, ClO}} -, NO 3 -, ▲ SO 2- 4 ▼
(Excluding the above), for example, acetate is preferable, and acetylacetonato complex in which the total number of charges is 0 as a result of coordination is also preferable.

Example 1 Tetramethoxyphthalocyanine of Reference Example 14 10 mg and 4 mg
Iodine was dispersed in 1 ml of chloroform and placed in a boat part 6 shown in the attached drawing, and naturally dried. By this operation,
A charge transfer complex is formed and the sublimability of iodine becomes almost negligible. Commercially available IT as a substrate for semiconductor layer formation
O Nesa glass (2.5 x 5 cm, thickness 1 mm, indicated by 3 in the figure)
Was placed 1 cm above 6 and 2 was 4.5 cm apart from 2'in the figure, and 4 was positioned between 3 and 6. Evacuate from the exhaust pipe indicated by 7 to 10 ^-1 torr, interrupt the exhaustion once, and 8
Argon gas was injected from the intake pipe indicated by, and this evacuation-injection operation was repeated three times, and then the degree of vacuum was maintained at 1 torr, and a current was supplied to 6 to heat to 300 ° C. After confirming that the sample has begun to adhere to the surface of the shutter plate indicated by 4, the current is passed so that a high frequency of 10W 13.56MHz is generated between 2-2 ', and after about 3 seconds the shutter plate is removed. 3 and 6
The position was shifted to the side from the middle position, and this state was maintained for 20 seconds, and the rear shutter plate was returned to the original position. Immediately, the high frequency wave and the heating source were cut off and the mixture was allowed to cool. Argon was injected into the apparatus to return to normal pressure, the substrate was taken out and placed in a high vacuum of 10 ⁻³ torr or less for one day. Place the substrate in a normal thermal evaporation system and deposit Amminium on the substrate in a 3.5 × 5 mm slit shape with a thickness of 150Å
Was vapor-deposited. After that, a part of the semiconductor layer was scraped off for elemental analysis, and a lead wire was placed on each of the exposed ITO surface and the aluminum layer to form an MSM element, which was connected to a DC conductivity measuring device. The voltage is swept at a rate of 2 mV / sec in the dark or under the irradiation of white light, the current value at that time is measured to obtain the voltage-current characteristics, various parameters are determined, and the characteristics of the MSM element are evaluated. went. Further, visible absorption spectrum measurement was performed on a portion where aluminum was not vapor-deposited. Further, the thickness of the semiconductor layer was determined with a stylus type surface roughness meter.

Elemental analysis of semiconductor layers (wt%): C59.03, H3.07, N16.46,
I17.92 Reference 1 Theoretical value of phthalocyanine: C74.99, H3.15, N21.86 Reference 2 Theoretical value of tetramethoxyphthalocyanine C68.35, H3.82, 17.71 Visible absorption spectrum: 950 nm or less Wide and featureless absorption Band (black-golden) Device characteristics: Dark: RR (value at 1V, the same applies below) 1.78.1
0 ³ , DP1.55, Voc0.82V, I _SC 0.92nA / cm ² Bright: Voc 0.77V, I _SC 1860nA / cm ² ff0.35, η4.
5 ・ 10 ^-2 % Semiconductor layer thickness: 185Å However, RR, DP, Voc, Isc, ff and η are rectification ratio, diode parameter, open circuit voltage, closed current, filactor and photoelectric conversion efficiency, respectively.

From the above, it was found that this MSM type element has good characteristics and can be used as a rectifying element, a diode, a photodiode and the like. In addition, this device is not destroyed even when a voltage of ± 20 V is applied and a current of 1.2 A / cm ^{2 is} applied. These characteristics did not change within ± 5% even after 30 days in dry air.

Next, the entire element was immersed in warm chloroform to completely extract iodine as a doping agent, and elemental analysis spectrum measurement was performed.

Elemental analysis of semiconductor layer (wt%): C72.35, H3.44, N20.11,
I0.03 Visible absorption spectrum (nm): 700, 666, 640, 602, 555 Almost no iodine embedded in the phthalocyanine bone nucleus is covalently engaged with it, and a charge transfer complex is formed. It can be seen that it is a physically strong embedded state. Also, from the results of elemental analysis and spectrum measurement, the polymerized phthalocyanine has lost about 2.5 R groups and is bonded and polymerized at the site, and the semiconductor layer has a ratio of the phthalocyanine skeleton and iodine molecules. X = 52%, y respectively
= 48% It seems that the structure is similar to the designated structural formula (2).

(False example 1 showing the novelty of the manufacturing method and MSM element of Example 1) The tetramethoxyphthalocyanine of Reference Example 14 was used in Example 1
It was thermally vapor-deposited on the same ITO Nesa glass as above, and the layer thickness was set to 170Å. This was put together with 2 g of iodine in a container having a reduced pressure of 10 ⁻³ torr and left for one day. The produced blackish golden vapor-deposited film-ITO NES glass was put into the vapor deposition apparatus again, and the pressure was reduced to 10 ⁻⁵ torr for vapor deposition of aluminum. Meanwhile, the black-gold color faded, and a clear iodine sublimation was observed. Then, aluminum was vapor-deposited (about 150Å thickness) in the same manner as in Example 1 to obtain an MSM element, and various parameters were obtained.

Elemental analysis of semiconductor layers (wt%): C71.46, H3.32, N20.03,
I2.44 Visible absorption spectrum (nm): 713 (wide), 670 (wide), 640sh, 605, 560 Reference Spectra before iodine doping: 702, 668, 642, 60
3,558 Device characteristics: Dark: RR2.0 ・ 10 ¹ , DP2.7, Voc0.63V, Is
c15.6nA / cm ² light: Voc0.55V, Isc230nA / cm ² ff0.18, η unmeasured (however, it was confirmed that it was 10 ⁻³ % or less) (production method of Example 1, novelty of MSM element) Example 2) showing the same as Example 1 except that the semiconductor layer was formed by vapor deposition of an equimolar mixture of tetramethoxyphthalocyanine and iodine of Reference Example 14 (about 160Å thickness).

Example 1 of falsified black-golden vapor-deposited film-ITO Nesa glass
Aluminum was vapor-deposited (about 150Å thickness) in the same manner as in, but during that time, the black gold color faded, and a clear iodine sublimation was observed.

Elemental analysis of semiconductor layer (wt%): C70.27, H3.08, N19.91,
I4.67 Visible absorption spectrum (nm): 720 (wide), 675 (wide), 643sh, 606, 560 Device characteristics: Dark: RR4.5, DP5 or more Voc0.31V, I _SC 35.6nA / cm ² bright Bottom: Voc 0.31V, I _SC 140nA / cm ² ff0.11, η10
^-5 % or less These characteristics are measured within 1 hour after making the device, and after leaving for about 3 hours or after applying DC voltage 1V
After 1.5 hours, it completely lost its rectifying property and became ohmic.

In the same manner as in Example 2-23 Example 1, except create S layer under the conditions shown in Table 4, the MSM element by thermal evaporation or high-frequency sputtering M _B thereafter, give the properties shown in Table 5 . Also,
Take transferred straight chain saturated fatty acid metal salt monolayer film on the air / water interface by the vertical dipping method or a horizontal deposition method on the S layer created under the conditions shown in Table 4, similarly further form M _B layer Let me
The characteristics shown in Table 6 were obtained as MIS type electrons. However, the heating method described in Table 4 represents the difference between heating the sample directly in the boat indicated by 6 in the accompanying drawings and by indirectly heating it by the heater indicated by 5.

From the elemental analysis values in Table 5, the constitution of the semiconductor layer is estimated as in Table 7.

From the results in Table 5, it can be seen that these MSM type devices have excellent characteristics and can be used as rectifying devices, diodes, photodiodes and the like. Further, from Table 6, it is understood that Voc and ff are generally improved in the MIS type element, and similarly excellent characteristics are exhibited. No changes in these properties were observed when left at room temperature under dry nitrogen for at least one week.

Example 24 Cobalt (II) tetra (tert-butoxy) of Reference Example 25
Phthalocyanine (500 mg) and iodine (300 mg) were treated in 3 ml of chloroform in the same manner as in Example 1 and then treated as in Example 1.
However, it was polymerized for 10 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 the polyvinyl alcohol, and the semiconductor layer was separated from the paper surface, and thoroughly washed in water. After measuring the surface roughness meter and visible absorption spectrum, platinum was formed on one side by high-frequency sputtering, and aluminum was formed on the opposite side by thermal evaporation to form a thin film to form a three-layer MSM type element, and its electrical characteristics were measured. The following results were obtained.

Elemental analysis of semiconductor layers (wt%): C54.62, H2.15, N16.93,
Co7.53, I16.92 Visible absorption spectrum: 950 nm or less Wide absorption band without features (black golden color) Device characteristics Dark: Voc 0.85V, Isc 0.32nA / cm ² , RR2.5
・ 10 ³ , under DP1.5: Voc 0.77V, Isc 1310nA / cm ² ff0.33, η3.6 ・ 10 ^-2 % Layer thickness: M _A (Pt) 510Å S 85.6 μm M _B (Al) 160Å From the elemental analysis, it was estimated that this semiconductor layer lost 3 R and was polymerized at that site, and the ratio of the phthalocyanine bone nucleus to the doping agent was 66/34. This element is in the form of a thin film having a total thickness of 100 μm or less, and has a feature that it can be cut into an arbitrary area and used as an element.

Example 25 A semiconductor layer was prepared in the same manner as in Example 24 except that 500 mg of ruthenium (II) tetra (1-methylbutoxy) phthalocyanine of Reference Example 27 was used, and platinum was further surface-coated by ordinary high frequency sputtering, _A single layer of cadmium arachidate was prepared by the same vertical peeling method as the M _A + S layer.
It was transferred from the air / water interface at dyn / cm, and aluminum was further thermally vapor deposited to obtain a MIS type device.

Elemental analysis of semiconductor layers (wt%): C55.16, H2.02, N14.33,
Ru12.5, I16.5 Visible absorption spectrum: 950 nm or less Wide characteristic absorption band (black golden color) Device characteristics Dark: Voc 0.85, Isc 0.23nA / cm ² , RR4.2
10 ³ , under DP1.5: Voc 0.79V, Isc 920nA / cm ² ff0.36, η4.6 ・ 10 ^-2 % Layer thickness: M _A (Pt) 730Å S 92.5μm M _B (Al) 140Å

[Brief description of drawings]

The accompanying drawings are schematic side sectional views showing an example of an apparatus for producing a semiconductor comprising a thin film of a phthalocyanine derivative polymerized with a doping agent according to the present invention. (Explanation of drawing numbers) 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 …… Semiconductor Substrate on which layers are created 4 …… Shutter (φ10 × 0.3cm) 5 …… Tungsten heater (It is written right above 6 in the figure, but actually it is diagonally above 6 at an angle of 60 ° from the vertical line. .
It will be installed at 5 cm. 6) Tungsten or tantalum boat (with the sample installed inside and 0.5 cm above the center line of 2'which also functions as a heater) 7 ... Exhaust pipe connected to the vacuum system 8 ...... Intake pipe connected to argon cylinder 9 ...... Teflon rubber O-ring 10 ...... Base 11 ...... Lead wires for supplying power to 2 and 2 ', 5 and 6

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Claims (10)

[Claims] 1. A specific phthalocyanine derivative represented by the following formula (1), iodine, SO ₃ , AsF ₅ , BF ₃ , SbF ₅ , and Nb.
F ₅ , TaF ₅ and PF ₅ selected from the group consisting of phthalocyanine derivative, equimolar amount to 1/10 molar amount of the active species generated by irradiating the mixed vapor with the doping agent with high frequency is smoothed. Polymerized with a doping agent, obtained by spontaneous polymerization on the substrate surface, thickness 20Å ~ 100μm
Phthalocyanine derivative thin film. However, R represents hydrogen, halogen, an alkoxy group of a straight chain or branched hydrocarbon having 5 or less carbon atoms, Me represents H ₂ , magnesium or a transition metal ion, and the substitution position of R is the isoindoline group of the above formula. In the 5-position or the 6-position. 2. A compound obtained by polymerizing a mixture of a phthalocyanine derivative of formula (1) and a doping agent at 300 to 400 ° C., 0.9 to 3 torr, high frequency output of 1 to 100 W, and polymerization time of 3 seconds to 7 minutes. A phthalocyanine derivative thin film according to item (1). 3. 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, a specific phthalocyanine derivative represented by the following formula (1), iodine, SO ₃ , and AsF ₅ are used as the semiconductor layer. , BF ₃ , Sb
F ₅ , NbF ₅ , TaF ₅ and PF ₅ , selected from the group consisting of phthalocyanine derivative, equimolar amount to 1/10 molar amount, active species generated by irradiating a mixed vapor with a doping agent with high frequency. To a smooth substrate surface and obtained by spontaneous polymerization, polymerized with a doping agent, thickness 20Å ~
An MSM type element or a MIS type element characterized by using a phthalocyanine derivative thin film of 100 μm. However, R represents hydrogen, halogen, an alkoxy group of a straight chain or branched hydrocarbon having 5 or less carbon atoms, Me represents H ₂ , magnesium or a transition metal ion, and the substitution position of R is 5 in the isoindoline group of the above formula. -Position or 6-position. 4. A phthalocyanine derivative thin film comprising a mixture of a phthalocyanine derivative of formula (1) and a doping agent.
The MSM type element or the MIS type element according to claim (3), which is obtained by polymerization at 0 to 400 ° C., 0.9 to 3 torr, high frequency output of 1 to 100 W, and polymerization time of 3 seconds to 7 minutes. 5. A phthalocyanine derivative thin film polymerized containing a doping agent, wherein the phthalocyanine derivative of the formula (1) is vaporized by heating under reduced pressure, and the vapor and a vapor of the doping agent are mixed in a high frequency wave. The active species produced by irradiating the surface of the substrate are introduced to a smooth surface of the substrate and spontaneously polymerized to obtain the active species.
The MSM type element or the MIS type element described in the item. 6. A conductive material having a large work function is indium tin oxide having a sheet resistance of 30 Ω / sq or less, graphite,
Glassy carbon, arsenic, selenium, germanium, palladium, tellurium, rhenium, iridium, platinum, gold,
The MSM type element or the MIS type element according to claim (3), which is selected from the group consisting of rhodium and ruthenium. 7. A conductive material having a low work function is beryllium, aluminum, scandium, titanium, manganese,
The MSM type element or MIS type element according to claim (3), which is selected from the group consisting of zirconium, antimony, lanthanides, thallium and lead. 8. The MIS according to claim 3, wherein the insulating layer comprises a metal salt of a linear saturated fatty acid having 16 to 22 carbon atoms.
Mold element. 9. The MIS type element according to claim 3, wherein the metal salt is a cadmium salt, a mercury salt, or an alkaline earth metal salt. 10. 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 deposition method. The MIS type element according to claim (3).