JPS60154682A - P-n homojunction element - Google Patents

Abstract

PURPOSE:To obtain preferable rectifying characteristic and durability by employing a non-amorphous acetylene polymer having specific value of higher of bulk density and using as a doping method of alkali metal an ion implanting method. CONSTITUTION:An acetylene polymer to be used has 0.7g/cc or higher of height density, and more preferably 0.8g/cc or higher and particularly more preferably 0.9g/cc or higher of non-amorphous material. If less than 0.7g/cc, a P-N junction element having preferable rectifying characteristic and durability is hardly obtained. The method of manufacturing the acetylene polymer is not particularly limited. The shape and the crystallinity of the polymer are not particularly limited, but high crystallinity having fibrous-fibril structure is preferable. A dopant for chemically doping includes various electron receiving compound known heretofore, i.e., halogen such as iodine, bromine and bromine iodide.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention involves chemically or electrochemically doping an acetylene polymer having a height density of 0.7 g/cc or more with a dopant to form a P-type aletylene polymer. The present invention relates to a P-n homojunction device having good rectification characteristics and durability, which is obtained by implanting alkali metal ions into the [ ) type alledylene polymer by an ion implantation method.

Since inorganic P-n homojunction devices are useful as electrical devices, many proposals have been made for P-n homojunction devices.

On the other hand, by doping the linear) 7 retylene polymer with Dovan 1~, its electrically conductive claws can be changed to 10-p.
~10: (C) is already known to be useful for electricity and electric cables because C can be freely controlled over a wide range of S/cn+. The rectifying properties are improved by mechanically applying a pressure of 8 f to a 1-] type acetylene high polymer film which is doped with 1 to 1!7. It is already known that a 1-11 small-7 junction element can be formed into a 1-1 (1) type of polymer film by chemically doping the dopan 1 in advance. It is known to chemically dope 1:' to create P-n junctions in a single adhesive 7 resin polymer film.

However, the alledylene polymer film used in these methods is the so-called Hakushu 7]' (Tokukosho/1g-
32581), the rectifying characteristics of the resulting P-n junction element are not necessarily satisfactory because the film is a porous Aledylene high vehicle body film with a J density of less than 0.7Q/cc. Not only is it not;
Durability, especially oxidation stability, was extremely low.

Moreover, when the porous film was chemically doped with Dopane I, the bond was destroyed due to migration of Dopane I when left for a long time. There was a phenomenon in which the rectification property 1<t deteriorated significantly.

The present inventors conducted various investigations in order to improve the drawbacks of the above-mentioned prior art, and as a result, they arrived at the present invention.

That is, the present invention provides j7 having a bulk density of ojg/cc or more.
Rectifying properties and durability obtained by chemically or electrochemically doping a dopant into a hytylene polymer to obtain a UP-type acetylene polymer, and then injecting alkali metal ions into the P-type acetylene polymer using an ion implantation method. 11
The present invention relates to a small P-n junction element with a good QI.

The 1)-1-ho seven junction element of the present invention has a height density of 0.7Q
/cc or higher is used, and ion implantation is used as the alkali metal doping method. 1,)
-11 homojunction element has better rectifying characteristics and durability. The acetylene high polymer used in the present invention has a height density of 0.7 g/cc or more, preferably 0.8 g/cc or more, and particularly preferably 0.8 g/cc or more.
．． It is a non-porous material with a weight of 9 g/cc or more. If the bulk density of the acetylene high polymer is less than 0.7 g/cC, it is difficult to form a p-n junction element with good rectification characteristics and durability.

There are no particular restrictions on the manufacturing method of the Ahidilene high and small platform having the above-mentioned high height density, but a specific example is JP-A No. 55-1.
No. 28419, No. 55-129404, No. 56-10
No. 428, No. 5G-63448, No. 56-13313
3 bows, No. 56-131636, No. 5G-115305
No. 57-53324, patent application No. 57-136826
No. 57-'136827, Special Publication No. 48-325
A method of pressure molding or stretch molding of the adilene high content material produced by the sawing method of No. 81, durability ujl! i6-4
Stretched acetylene high polymer obtained by the method of No. 5365, powdered acetylene high 4 obtained by the method of Patent Application No. 57 147717 @ Kasa (combination is molded under pressure - I
1) A method for obtaining a high bulk density AJ-len high-density base from a U-tyrene high polymer, a Rutzteinger catalyst, a metathesis catalyst, etc. A method of adding 1 q of acetylene high polymer obtained by using acetylene high polymer with high bulk density ('! I can give you something.

There are no particular limitations on the shape, crystallinity, etc. of the acetylene polymer used in the present invention C, but it is preferably a highly crystalline polymer having a 11-shaped microcrystalline (fibril) structure. The doping method for manufacturing the [Y] type aretylene high vehicle assembly may be either chemical doping A3 or electrochemical doping.

Chemical doping-4 dobans 1 to 4 include conventionally known electron-accepting compounds, namely (I) halogens such as iodine, bromine and bromine iodide, (n) arsenic pentafluoride, Metal halides such as anti-sulfuric acid pentafluoride, iridium tetrafluoride, phosphorus, phosphorus perfluoride, aluminum chloride, aluminum bromide and aluminum fluoride, (m) sulfuric acid , nitric acid, full A sulfuric acid, 1~
Riful A romethane sulfur M tj , J, H') a ml
5J'+ MO(7) Like D h n u, (IV
)E Indium oxide, nitrogen dioxide, diflu'A [1 sulfonyl bar A oxide, oxidizing agent such as oxygen, (V)Aa
0 Sentence 04, (Vl)
-11-lacyanoquinodimethane, talolanil, 2,3
-dichloro-5,6-dicyj/noparabenzo4non, 2
゜3 Nbromo 5,6-shishi 7 Novara benzoquinone can be mentioned.

On the other hand, if the dopant is electrochemically doped -C
(i) PF2, 5bFe, AsF3゜5bc
i; a halide anion of a group Va element such as BF;
Halide anions of elements of group 1lla such as 3, I
-<Ia), Bl', Cku- such as halogen animate A
Examples include, but are not limited to, anions such as oxalic acid anions such as -n, C and 0;, but are not necessarily limited to these.

A specific example of a compound that provides the above-mentioned anion dopane 1- is iPF6. Li Sb Fs, l
-iΔS [2 a, Li C101, Na 1
．． Na PFa.

Na3bFa, NaΔSFe, NaCf
1-0<, KI, KP "o, KSb Fa, to ΔSF6.KO Oq, ((n-Bu)4N)"
・(AsFe)-.

[(ro-Bu)iN)'' ・ (1] FB )-, (
<n13u)4 N)" ・C9-0: , LI A
uC1<.

Li 13Fi , No-As Fe , NO2・As
Fa.

No-BF4, NO2・BF4, No-PF5
C can be mentioned, but it is not necessarily limited to these. These Dopanes 1 to 1 may be used alone or in combination of two or more.

Anion dopants other than the above include 1-IF
There is 2A and 2A.

It is desirable that the doping level of Dovan 1 to 2 is 20 mol % or less, preferably 0.01 to 15 mol %, per repeating llj position (CH) of the ahithylene polymer.

Method 1: Adding ions to a P-type alethylene high-vehicle combination chemically or electrochemically doped with a dopant.
There are no particular restrictions, and in general, ions accelerated to several KV-・several hundred+<V are adopted. From the viewpoint of suppressing the reaction, it is preferable that the accelerating voltage is 150 KV or more.
It is particularly preferable that 1001<V or less. As the ion source, a high frequency discharge type, an electron impact type, or a γ-1Δ-1Δ plasma 1 Heron type qll type can be used.

In the present invention, an alkali metal ion is used as the ion. A specific example of an alkali metal ion is L
il, Na-to, K”, Rb).

Each ion of O5+ can be mentioned.

The implantation h1 of alkali metal ions is desirably 20 mol % or more, preferably 0.01 to 15 mol %, per repeating unit (CI-1) of the alebrene high polymer.

The p-n photo-E junction element of the present invention has good 4T rectification characteristics and good durability, especially oxidation stability.
It is extremely useful as an electric/electronic element, and can be used as specific examples such as 1~Run Sister, solar cells, etc.

Hereinafter, the present invention will be explained in detail with reference to Examples.

Example 1 [A for achieving high height density [¥4J construction of Bren high polymer] In a straight glass reaction vessel that was completely replaced with nitrogen gas,
Purification was carried out according to a conventional method using a polymerization solvent (Helton 200).
ml, as a catalyst 1~rhabdoxytitanium 2.
94 millimeters and 1 to riegil aluminum 1.34
A catalyst solution was prepared by sequentially charging milli7yl at room temperature.

The catalyst solution was a homogeneous solution. Next, the reaction vessel was cooled with liquid nitrogen, and the nitrogen gas in the system was exhausted using a vacuum pump. The reaction vessel was cooled to −78°0, and while the catalyst solution was left still, purified acerene gas at a pressure of 1 atm was blown into the reactor. At the beginning of polymerization, the entire system became agar-like. The polymerization reaction was continued for 10 hours while maintaining the pressure of the alebrene gas at 1 atm. The system was agar-like with a reddish-purple color. After the polymerization was completed, unreacted aleben gas was removed, and 200 mQ of purification 1 was carried out while keeping the temperature of the system at -78°C.
- Washing was repeated four times with toluene to obtain a swollen acetylene polymer having a film thickness of about 0.5 cm. This swollen allebrene high polymer has a molecular weight of 300 to 5
It was a swollen product in which fibrous microcrystals (fibrils) with a diameter of 0'0 were regularly intertwined, and no powdery polymer was formed. The polymer was sandwiched between sticky Fuconiro plates, pre-pressed at room temperature with a pressure horn of 100 kQ/・HI3, and then high-pressure pressed at a pressure of 15 tons 7 cm2 to form a uniform and flexible product with a reddish-brown metallic luster. A certain film thickness 1
A 20 μm film of ab'frene high polymer was obtained.

This film is 511. It was vacuum dried for 1 hour at room temperature. The vacuole of the obtained alebrene high polymer film was 1.0.
At 5 g/cc, electron microscopy revealed that the film was non-porous.

In addition, this acetylene high-medium polymer film has a cis content of 9
The electrical conductivity at 0% and 20° C. (DC 4p:; 1 child method) was 4.8×H1-'Ω-1.Cll1-1 type half.

[Doping Experiment J] Acebrane high polymer film with a film thickness of 120μ and a height density of 1.05 g/cc obtained by the above method,
A small piece with a width of 0.5cIll and a length of 2.0CI11 was cut out and mechanically crimped and fixed to a platinum wire to serve as a positive electrode. Lidium metal was used as a negative electrode, and the temperature of LiC or 01 was set to 0.
Doping was carried out for 15 hours under constant current (0.09 mA) using a 3 mol/day propylene carbonate solution as the electrolyte. After the doping was completed, the doped acebrene polymer film was washed with [J-Birenno J-Bone 1~]. Doped Aceblen high car combination fill lX
& indicates a golden metallic luster, and elemental analysis revealed that the composition was a P-type semiconductor with a conductivity (direct current four terminal method) of 320Q-'-am-1.

[Ion implantation and rectification characteristics experiment] One type A obtained by the above method was made by using a high frequency discharge type as an ion source on one side of the dylene heavy content film, and
Dose F) at accelerating voltage -50KV
x = 6x101 et Cm-2 (noy Δn injection, 1)
-rl homozygous devices were produced. After the ion treatment was completed, gold was deposited on it to form a mandrel, as shown in Figure 1.

Figure 1 shows gold 711 'I' which is a specific example of the present invention.
j 1) nij・[This is a cross-sectional schematic diagram of a bonding element, and 1
t, is conductive (2 is a P type doped with C Oλ) 2 is a retylene high polymer part, 3 is an n type ahytylene high medium polymer part doped with Na''.

Using the gold tta 41) r) homojunction element fabricated in this way, we applied a voltage to both ends of this junction element and measured the flowing current value to investigate the relationship between voltage and current. The rectification ratio in the application type J-■-ga/IV was 2/10-r1, and j! The rectification ratio of the blown P-n homojunction device after being left in the air for 7 days was 225.

Comparative Example 1 [Manufacture of acebrene high polymer] In a glass reaction vessel with an internal volume of 500 i under a nitrogen atmosphere,
5.11n! 1 (15,099 mol) of titanium phenylene chloride was added and dissolved in 20.0+ m toluene, then 5.4 mR < 40 mmol) of 1
- Riedyl aluminum was added with stirring to prepare a C reaction catalyst solution.

The reaction vessel was cooled with liquid nitrogen, the nitrogen gas in the system was evacuated using a vacuum pump, and then the reaction vessel was cooled to -78°C.

After avoiding rotation of the reaction vessel to prevent the catalyst solution from adhering uniformly to the inner wall of the reaction vessel, immediately add 1
Polymerization was initiated by introducing purified acetylene gas at a pressure of atmospheric pressure. Simultaneously with the polymerization fl, an acetylene high polymer with metallic luster precipitated on the inner wall of the reaction vessel. After the polymerization reaction was carried out for 1 hour at a temperature of -78 DEG C. while maintaining the pressure of alleburene at 1 atm, the unreacted abrane was evacuated with a vacuum pump to stop the polymerization. After removing the residual catalyst solution with a syringe under a nitrogen atmosphere, purification was carried out while keeping it at -78 °C.
The catalyst solution was washed 6 times with 1oo7 of luene, and then dried under vacuum at air temperature. % film-like acetylene polymer was obtained.This film-like acetylene polymer had an electrical conductivity of 2.5.
x 1 8Ω-'-Hl-1 was present.The height density of this film-like aceblene polymer was 0.52 (J/CC). Electron microscopy observation J: Riko's membranous alebrene polymer was porous with ibrils intertwined in a disordered manner.

"Doping experiment" The porous material obtained by the above method has a height density of 0.52a/
The composition was changed to (C1-1(
C01)] Conductive film-like A060 15 layers of high polymer. Kou 9den 1<J-Its
j-shaped 'j' I? Brene high polymer has an electrical conductivity of 290
It was a P-type semiconductor of 0-1·cnji1.

Ion implantation and rectification property experiment] [1] using the above 1j method as an alledylene polymer of type 1! A Pn homojunction device was fabricated by injecting Na➝➝ in the same manner as in Example 1 except that a porous film-like acetylene high-vehicle assembly was used.

Hereinafter, rectification characteristics were measured in exactly the same manner as in Example 1. As a result, the rectification ratio was 62 when the applied voltage was ±4V. Ma lζ, i! The rectification ratio of the Pn homojunction device after leaving it in air for 7 hours was 14.

Chemical Comparative Example 2 A non-porous aceblene polymer film doped with the C-cross Oλ ions prepared in Example 1 was single-sidedly doped to produce a Pn homojunction device. The rectification characteristics of this junction element were measured in exactly the same manner as in Example 1.

As a result of (a), the rectification ratio was 53 when the applied voltage was ±4V. In addition, the assembled P-n homojunction element is 71'' in the air.
After several ia, the junction was broken and no rectifying properties were exhibited.

Example 2 The non-porous acebrene polymer film obtained in Example 1 was doped with iodine by contacting it with iodine vapor and the electrical conductivity of the iodine-doped film was 2 x 10-3 C)-1 cm. −＋
A P-type semiconductor was obtained. A high-frequency discharge type ion source was used as an ion source on one side of the I) type Aledilene high vehicle assembly film, and K' was dosed at an accelerating electric current of 12 KV.
) A homojunction device with a thickness of 3 x 1016 cm-2 (with a noise injection method of 1) was fabricated. Gold was vapor-deposited on this junction element in the same manner as in Example 1, and its rectification characteristics were examined. As a result, the rectification ratio is 207 when the applied voltage is ↓4V.
Met. Also, cypress! The I81! flow ratio was 19:( after the P-") small bonded element was left in the air for 7 days.

[Brief explanation of drawings]

FIG. 1 is a schematic cross-sectional view of a metal vapor-deposited 1)n homojunction element which is a single example of the present invention; This is a diagram showing the relationship between the current and the current of the current +11 measured using the 1. 1Non 11) Polymer part 3...N-type acetylene high polymer part injected with Na+

Claims (1)

[Claims] Dopanes 1 to 1 are chemically or electrochemically doped into an acetylene polymer having a height density of 0.79/cc or higher to obtain a P-type acetylene polymer, and then the P-type acetylene polymer is subjected to ion implantation. 1)-[] homojunction device formed by implanting alkali metal ions.