JPS6216490A - Semiconductor - Google Patents

Abstract

PURPOSE:To provide a semiconductor capable of controlling the conductivity from insulating material to an excellent semiconductor by adjusting the amount of dopant, and having excellent stability and handleability, by doping a specific organometallic complex with a halogen. CONSTITUTION:An organometallic complex of formula MXmLn (M is group IV, V or VIII metal; X is halogen; L is phosphine, isocyanide or cyclopentadienyl; m is 1 or 2; n is 1-4) [e.g. TiCl2(C2H5)2] is doped with a halogen (preferably iodine) preferably at 0-50 deg.C to obtain the objective semicon ductor. The complex is used in crystalline or powdery form, etc. The amount of the dopant is preferqably 0.02-200mol% based on the organometallic com plex.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a highly stable semiconductor obtained by doping a specific organometallic complex with halogen.

[Conventional technology]

Conventionally, it has been known that polyacetylene, polyparaphenylene, polyphenylene sulfide, polythenylene, and non-polymerized polymers exhibit good electrical conductivity, and that they change from an insulator to a semiconductor to a conductor by changing the amount of doping.

On the other hand, charge transfer complexes such as tetrathiafulvalene-nato-2-cyanoquinodimethane and beryrezi-iodine are known as non-polymer-based conductive materials.

[Problem that the invention seeks to solve]

It is generally known that doped conductors are unstable in air, resulting in lower conductivity and material deterioration. In this connection, it is desired to develop a stable conductor that does not cause a decrease in IE conductivity or material deterioration.

An object of the present invention is to provide a novel electrical conductor that is highly stable in air and easy to handle.

[Means for solving problems]

In view of these shortcomings, the present inventors conducted various studies in order to obtain a new, more stable conductor, and as a result, if they selected a specific non-polymer-based organometallic complex and doped it with halogen, it would be possible to create a semiconductor. The present invention has been achieved by discovering that a novel electrical conductor with good stability having the following properties can be obtained.

That is, the present invention is based on the general formula (1) % formula % () (where M represents a metal of Group D, Group 5 or Group A of the periodic table, X represents a halogen, L represents a phosphine, Incyanide, represents a cyclopentadienyl group, m is /
Alternatively, 2 and n represent an integer of 1 to 4. ) It consists in a semiconductor obtained by doping an organometallic complex represented by halogen with halogen.

The present invention will be explained in more detail below.

In the present invention, as described above, the organometallic complex represented by the general formula (1) is used.

In the general formula (1), M is a metal of Group 4 of the periodic table such as titanium, zirconium, and hafnium, a metal of Group 5 of the periodic table such as vanadium, a metal of Group 5 such as cobalt, nickel, iron, palladium, and platinum. metals of the group.

Examples of X include halogens such as chlorine, bromine, and iodine.

L is triphenylphosphine, phosphine such as triethylphosphine, triphthylphosphine, diphenylphosphine, diphenylphosphine, methyl isocyanide, n-
Examples include incyanides such as phenyl cyanide, t-butyl isocyanide, phenyl cyanide, and tolyl isocyanide, and cyclopentadienyl groups.

m is an integer of / and n is an integer of / to g. Specific organometallic complexes represented by the general formula (1) include bis(triphenylphosphine)iron cyclo2ide, bis(triphenylphosphine)iron dyglomite, his(triethylphosphine)cobalt dichloride, bis(triphenylphosphine)iron diglomite, and bis(triphenylphosphine)iron diglomite. phosphine) cobalt dichloride, tetrakis(tolylisocyanide) cobalt diiodide, tetrakis(t-butyl incyanide) cobalt dichloride, cyclopentadienyl(triphenylphosphine) cobalt diiodide, bis(trilysocyanide) phenylphosphine) nickel dichloride, bis(triphenylphosphine) nickel dichloride, cyclopentadienyl (triphenylphosphine) nickel chloride,
Bis(diphenylphosphinoethane) nickel dichloride, bis(diphenylphosphinoethane) nickel diiodide, bis(tolyl isocyanide nickel)
Cyclolide, bis(triphenylphosphine)palladium dichloride, bis(triphenylphosphine)palladium siaiotide, bis(triphenylphosphine)platinum dichlorite, bis(triphenylphosphine)platinum dichloride, bis(cyclopenta Dienyl) titanium dichloride, bis(cyclopentadienyl) zirconium cyclo2ide, bis(cyclopentadienyl) hafnium dichloride, bis(cyclopentadienyl) vanadium dichloride, and the like.

Especially cyclopentadienyl (triphenylphosphine)
Nickel chloride, bis(triphenylphosphine)
Cobalt dichloride, bis(triphenylphosphine)cobalt diiodide, bis(triphenylphosphine)nickel dichloride, and the like are suitable.

Such organometallic complexes are generally solid at room temperature and can be synthesized relatively easily using known techniques or applied techniques thereof.

For example, New Experimental Chemistry Course Volume 7.2, Organometallic Chemistry P7? −
94t contains titanium zirconium, hafnium complex, P
loo is a vanadium complex, P/4t/ -P2≦2
(/ri76) etc. contain cobalt, nickel, iron, etc.? A method for the synthesis of organometallic complexes of group metals is described.

In the present invention, chlorine, bromine and iodine are used as halogens for doping the organometallic complex, and iodine is preferred.

Doping is carried out in accordance with the usual method by forming the organometallic complex into a shape that is easy to dope, such as crystal, powder, compact, or thin film, and placing it in a gas or liquid phase atmosphere.
0~70℃, preferably θ~! It may be carried out at 0°C.

The cap of the doping agent is 0.0. θ
/~300 mole percent, preferably 0.02-20
It is about 0 mole percent.

The organometallic complex of the present invention doped with halogen as described above exhibits good semiconductivity from an insulator by varying the doping amount, exhibits good stability, and is easy to handle.

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

〔Example〕

Synthesis Example-/(Complex of Example-/) A comole of triphenylphosphine O0θ is dissolved in a small amount of hot anhydrous alcohol, and 0.01 mole of copal chloride dissolved in hot anhydrous alcohol is added thereto. Recrystallizing the crystals obtained by cooling and filtering from hot alcohol is quantitatively OOO'l.

(P('aHJs)t was obtained.

Synthesis Example-2 (Example-complex of λ) 0.03 mol of titanium tetrachloride and methylene chloride in an argon-substituted flask! ? - and cool the outside with ice. When tetrahydrofuran/θd is added dropwise with stirring, yellow crystals of Ti11,·2T)IF are obtained. This is 0102
The mixture was externally water-cooled under argon with 10 td of cyclopentadienyl sodium O0O and 10 td of sodium cyclopentadienyl sodium, and a solution of 4 t mole of cyclopentadienyl sodium O0O in tetrahydrofuran was added dropwise with stirring. After the addition was completed, the mixture was further stirred at room temperature for 2 hours, and then the solvent was distilled off under reduced pressure, and the resulting residue was extracted with chloroform using a Soxhlet extractor. Recrystallization from chloroform gave yellow-orange crystals T1012(0,H,)2.

Synthesis Examples 3 to 22 The organometallic complexes shown in Examples 3 to 22 in Table 1 were each synthesized according to the known method described above (described in Shin Jikken Kagaku Koza Vol. 72). Incidentally, since these can be easily manufactured by known methods, the detailed manufacturing method will be omitted.

Example/-, 24 The crystal or powder of the synthesized organometallic complex was molded under vacuum using a pellet molder for infrared absorption spectrum measurement.
Molded under pressure (approximately tokg weight/-) (diameter/3 dragons,
Thickness 0O-t1! l) or apply a solution of the organometallic complex on a glass plate and after drying, form a thin film (θ, /μα~
7000 μo11) was used. A platinum wire is attached as an electrode to the obtained pellet or thin film using a conductive dot tie (KO-/2).

After measuring the conductivity of the undoped sample, it was placed in a desiccator containing iodine at room temperature, and the sample was doped with iodine by sublimation.

The amount of iodine doped was calculated by measuring the weight increase of the sample. The amount of iodine doped into the metal was as shown in Table 1. Depending on the amount of dope, the samples exhibited yellow to brown to black colors, and no change in conductivity was observed even when the doped samples were left in the air at room temperature in a sealed container. The electrical strength of each sample was measured by the known four-terminal method. The results are shown in Table-7.

Table - [Effects] The halogen-doped organic gold II4 ingot of the present invention exhibits good semiconductivity from an insulator due to the change in doping violet, has good compatibility, and is easy to handle. Electronics, photographic recording materials, solid-state displays, optical memory +,
It can be applied to a wide range of fields such as terminal equipment, antistatic materials, photoelectric conversion elements, and storage batteries.

Sender: Mitsubishi Chemical Industries, Ltd. Representative Patent Attorney Yokoya - (1 other person)

Claims (1)

[Claims] (1) General formula MX_mL_n (where M represents a metal of Group 4, Group 5 or Group 8 of the periodic table, X represents a halogen, L represents a phosphine, isocyanide, or cyclopentadienyl group, m is 1
or 2, n represents an integer from 1 to 4) A semiconductor obtained by doping an organometallic complex represented by halogen with halogen.