JP4182197B2 - Generation of chalcogenide elements - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for generating a chalcogenide element used for production of a thin film or fine particles containing the chalcogenide element.
[0002]
[Prior art]
Currently, in the production of solar cells containing chalcogenide elements, thin films such as compound semiconductors, and fine particles, chalcogenide elements are generated mainly by thermal decomposition or photolysis of symmetric dialkyl chalcogenide compounds. (DJ Cole-Hamilton, Chem. Commun., 1999, 759)
In the production of thin films and fine particles such as compound semiconductors containing chalcogenide elements, the thermal decomposition or photolysis reaction of the symmetric dialkyl chalcogenide compound is usually carried out in the gas phase, so as a symmetric dialkyl chalcogenide compound, in many cases It is necessary to use a highly volatile material (ibid.).
[0003]
However, these alkyl chalcogenide compounds are known to be toxic. In particular, selenium compounds are highly toxic, so the use of highly volatile organic chalcogenide compounds has considerable operational safety problems. Yes.
In addition, production processes of thin films such as compound semiconductors containing chalcogenide elements, fine particles, and the like are often performed at high temperatures, and thus have a drawback of being an energy intensive process.
[0004]
Attempts have also been made to generate chalcogenide elements by photolysis, but these symmetric dialkyl chalcogenide compounds have a problem of requiring a long reaction time because of their low photoreactivity. Furthermore, dibenzyl chalcogenide is known as a highly photoreactive symmetric dialkyl chalcogenide compound, but dibenzyl chalcogenide is a thermally and photochemically very unstable compound, and it is suitable for use in ordinary production sites. Has the problem of being extremely difficult.
[0005]
[Problems to be solved by the invention]
This invention is made | formed in view of the above-mentioned actual condition in a prior art. That is, an object of the present invention is to provide a simple method for generating a chalcogenide element that uses a low-volatile and thermally stable organic chalcogenide compound as a raw material, has high operational safety, and does not require high-temperature treatment.
[0006]
[Means for Solving the Problems]
The present inventors have conducted extensive research to overcome difficulties in the production of thin films and fine particles of chalcogenide elements alone, or thin films and fine particles containing chalcogenide elements. As a result, simple treatment of specific organic chalcogenide compounds at low temperatures has been achieved. It has been found that a chalcogenide element is easily generated by application, and the present invention has been completed based on this finding.
[0007]
That is, the present invention is a method of generating chalcogenide element, wherein the ultraviolet or the organic chalcogenide compounds for irradiating a laser beam represented by the following general formula (1).
Ar ¹ XR ¹ (1)
(In the formula, X represents selenium or tellurium. R ¹ represents an optionally substituted chain or alicyclic hydrocarbon group, a condensed polycyclic aromatic hydrocarbon group, or a substituted aromatic hydrocarbon group; Ar ¹ represents an optionally substituted aromatic hydrocarbon group.)
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to a low-volatile organic chalcogenide compound having a specific chemical structure in a method for producing a thin film, fine particles, etc., such as a compound semiconductor formed by a chalcogenide element alone or including other components in the chalcogenide element. By performing a simple treatment of irradiating with ultraviolet rays , chalcogenide elements are easily generated safely at low temperatures.
[0009]
The organic chalcogenide compound used in the present invention is one or more selected from the chemical structural formula represented by the above general formula (1), and at least one of the chalcogenide elements may be substituted with an aromatic hydrocarbon group It has a chemical structure in which the aromatic rings are directly bonded.
Organic chalcogenide compounds in which an aromatic ring is directly bonded to these chalcogenide elements have a hydrocarbon group larger than phenyl bonded to at least one of the chalcogenide elements, compared to dialkyl chalcogenides, which are currently generally used with a small number of carbon atoms. molecular weight is increased volatility is reduced to the effect of this becomes remarkable as the molecular weight increases by changing the compound (1). When the compounds become low volatility in this way, the amount taken into the human body by sucking the vapors of these compounds is reduced, and safety is increased. Furthermore, even when these compounds are scattered due to an accident or the like, the concentration of the compounds in the atmosphere can be kept low, which is optimal for ensuring safety in an emergency.
Since these organic chalcogenide compounds have an aromatic hydrocarbon group in at least one of the chalcogenide elements, the absorption efficiency of ultraviolet rays is increased. As a result, the efficiency of the decomposition reaction of the organic chalcogenide compound due to the absorption of ultraviolet rays can be increased, and the generation of the chalcogenide element by this decomposition reaction can be performed at a low temperature within a short time.
In addition, dibenzyl chalcogenide, which has been studied at the laboratory level, is extremely low in thermal and photochemical stability because the chalcogenide atom is bonded to two highly reactive benzylic positions. Handling this compound in the field is extremely difficult. On the other hand, the organic chalcogenide compound used in the present invention has excellent thermal stability and moderate photochemical stability because the chalcogenide atom is not directly bonded to a highly reactive benzyl position or the like. It has properties and does not exhibit thermal or photochemical instability that would be a disadvantage when used in production sites as found in conventional dibenzyl chalcogenides.
[0010]
In the organic chalcogenide compound represented by the general formula (1) used in the method of the present invention, X of the chalcogenide element is selenium or tellurium. Moreover, the chain or alicyclic hydrocarbon group which may be substituted may be any group having a function of reducing volatility or improving thermal stability, and preferably has 1 to 40 carbon atoms. Preferred examples include straight-chain or branched chain hydrocarbons having 1 to 15 carbon atoms, or cyclic hydrocarbons having 1 to 40 carbon atoms, more preferably 1 to 15 carbon atoms. It is not limited. Moreover, the aromatic hydrocarbon group which may be substituted represented as Ar ¹ has a good absorption efficiency of ultraviolet rays, and has an action of reducing volatility or improving thermal stability. Any substituent may be used as long as it has a carbon number of preferably 6 to 40, more preferably 6 to 20, but is not necessarily limited thereto.
[0011]
Further, the optionally substituted chain or alicyclic hydrocarbon group includes an aromatic hydrocarbon group and an aromatic carbon group substituted with various functional groups including heteroatoms such as O, N, and S. The aromatic hydrocarbon group that contains a hydrogen group and may be substituted includes a chain or alicyclic hydrocarbon group, and various functional groups containing a hetero atom such as O, N, and S. Substituted ones are also included. Furthermore, the optionally substituted aromatic hydrocarbon group further includes a heterocycle containing a hetero atom typified by pyridine, furan and the like as a partial structure. In addition, when the substituent which may be substituted by these chain or alicyclic hydrocarbon group and aromatic hydrocarbon group is a functional group or hydrocarbon group containing a carbon atom, it is included in the substituent. The number of carbons generated is not included in the number of carbons.
[0012]
These substituents are not particularly limited, but those that adversely affect the reactivity of the organic chalcogenide compound, the thin film and fine particles made of the generated chalcogenide element, and the thin film and fine particles containing the chalcogenide element are excluded.
[0013]
Examples of the organic chalcogenide compound preferably used in the present invention include methylphenyl chalcogenide, ethylphenyl chalcogenide, propylphenyl chalcogenide, butylphenyl chalcogenide, pentylphenyl chalcogenide, hexylphenyl chalcogenide, cyclopentylphenyl chalcogenide, cyclohexylphenyl chalcogenide, diphenylchalcogenide, diphenylchalcogenide, , Methallylphenyl chalcogenide, 1,2-bis (phenylchalcogeno) ethane, 1,3-bis (phenylchalcogeno) propane, and the like.
[0014]
The organic chalcogenide compound represented by the general formula (1) may be used alone, but may be used by dissolving or mixing it in a solvent that does not significantly inhibit the generation of chalcogenide elements by ultraviolet irradiation of the organic chalcogenide compound. it can. As the solvent, water, alcohols, linear or cyclic alkanes, solvents such as ethers that transmit ultraviolet rays, or a mixed solvent thereof can be used.
[0015]
When the organic chalcogenide compound is used by mixing with a solvent, it can be used by mixing at an appropriate ratio, and the mixing ratio is not particularly limited. Further, when the organic chalcogenide compound is used by dissolving in a solvent, the concentration is not particularly limited and may be not more than the saturated concentration of the organic chalcogenide compound with respect to the solvent, but preferably 0 to 100% by weight with respect to the solvent. More preferably, the content is 0 to 30% by weight.
[0016]
In order to generate a chalcogenide element in the present invention, an organic chalcogenide compound, a solution thereof or a mixture of the compound and a solvent is attached to the substrate surface by dipping or spraying, and the organic chalcogenide compound contains a solvent or a solvent. A thin film with the film removed may be formed on the surface of the substrate, and ultraviolet irradiation may be performed while the substrate is stationary or moving. Alternatively, the substrate may be submerged in the liquid of the organic chalcogenide compound or the solution of the organic chalcogenide compound, and ultraviolet irradiation may be performed in a state where the substrate is stationary or moving.
[0017]
In addition, an organic chalcogenide compound, a solution thereof, or a mixture of the compound and a solvent is attached so as to form a pattern on the substrate surface by printing or lithography, and the organic chalcogenide compound contains the solvent or the solvent is removed. By forming a thin film in a state on the surface of the substrate and irradiating with ultraviolet rays while the substrate is stationary or moving, the chalcogenide element can be generated in a fine pattern.
[0018]
In the present invention, the temperature at which ultraviolet rays are irradiated is not particularly limited, and the organic chalcogenide compound represented by the general formula (1) used, a solution of the organic chalcogenide compound, or a mixture of the organic chalcogenide compound and a solvent is used. However, it is preferably −80 ° C. to 100 ° C., more preferably 0 to 50 ° C.
[0019]
There is no restriction | limiting in particular as a light source used for irradiation of this invention, Normal light sources, such as a low pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, various excimer lamps, etc. can be used. The irradiation light intensity is not particularly limited, but a light source of 0.1 mW to 10 kW is suitable as light.
[0020]
A laser can also be used as the light source. The laser light source is not particularly limited, and the laser light may be pulsed light or continuous irradiation light, but excimer laser (ArF, KrF, XeCl, XeF, F ₂ etc.), argon ion laser, krypton ion laser, YAG laser (harmonic) Wave) or the like. Although there is no restriction | limiting in particular also in laser irradiation light intensity | strength, 0.1 mJ / pulse-1 kJ / pulse is suitable for pulse light, and 0.1 mW-10 kW light source is suitable for continuous light.
[0021]
The light irradiation time is appropriately determined in consideration of the structure of the organic chalcogenide compound, the type and intensity of ultraviolet rays, and it is usually sufficient for 10 minutes. After the irradiation with ultraviolet rays, the unreacted organic chalcogenide compound and the compound produced by the ultraviolet reaction, etc. are removed by a solvent, vacuum treatment or the like, whereby the production of the chalcogenide thin film and the thin film containing chalcogenide can be completed.
[0022]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited at all by these Examples.
Example 1
A hexane solution of 10% by weight of pentylphenyl telluride is coated on the surface of the glass substrate, air is blown at room temperature for about 1 minute to evaporate the solvent, and then the krypton fluorine excimer laser (100 mJ / 100 m) is applied to the glass surface. cm 2 ^· pulse, 1 Hz) and 7 pulse irradiation at room temperature, then, when the glass substrate was dried and washed with hexane, thickness 0.05mm following silvery mirror-like tellurium thin film was formed on the glass substrate surface . When this was subjected to a peeling test using cello tape, peeling of the thin film did not occur.
[0023]
【The invention's effect】
According to the present invention, when producing a thin film or fine particles used for a fuel cell or a compound semiconductor containing a chalcogenide element alone or containing a chalcogenide element, the low-volatility, low toxicity, and stable organic chalcogenide compound is used. Can generate chalcogenide elements, and can be easily and safely operated with low energy, which is extremely useful for industrial implementation.

Claims (1)

A method for generating a chalcogenide element, which comprises irradiating an organic chalcogenide compound represented by the following general formula (1) with ultraviolet rays or a laser beam thereof.
          Ar ¹ XR ¹                                       (1)
(In the formula, X represents selenium or tellurium. R ¹ Represents an optionally substituted chain or alicyclic hydrocarbon group, a condensed polycyclic aromatic hydrocarbon group or a substituted aromatic hydrocarbon group, Ar ¹ Represents an optionally substituted aromatic hydrocarbon group. )