JP3313129B2 - Graphite structure carbon intercalation compound, its production method and thermoelectric conversion element - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a graphite structure carbon interlayer.
The present invention relates to a compound, a method for producing the compound, and a thermoelectric conversion element .

[0002]

2. Description of the Related Art A gas phase pyrolysis method is one of the typical methods for producing graphite-structured carbon. In this method, a raw material is introduced into a reaction chamber provided with a substrate together with a carrier gas, and the entire reaction chamber is heated, or the substrate is heated to form pyrolytic carbon on the substrate.

FIG. 6 is a diagram showing the relationship between the plane spacing of graphite-structured carbon synthesized on a nickel substrate by a conventional method using propane as a raw material and the substrate temperature during synthesis. In this figure, at a substrate temperature of 500 to 700 ° C., the surface spacing is 3.85 to 4.0 °,
The temperature is about 3.5 ° at 1000 ° C., and the higher the temperature becomes, the smaller the plane spacing becomes, and there is a boundary area around 800 ° C.
As described above, in general, in the synthesis of carbon by gas phase pyrolysis, as the substrate temperature increases, the crystallinity of the synthesized graphite structure carbon improves. Therefore, in order to synthesize high-quality graphite-structured carbon having high crystallinity, it is necessary to synthesize at a high temperature, and a high-temperature-resistant substrate is required.

[0004] Therefore, it will be understood that if high-quality graphite-structured carbon can be synthesized at a lower temperature than conventional, there is an industrial merit. On the other hand, the present inventors have proposed a method of producing a graphite intercalation compound by pyrolysis of an organic compound of a heavy metal such as lead or tin in the above-mentioned vapor phase pyrolysis (US Pat. No. 4,714,63).
9), titanium (Ti), vanadium (V), chromium (C
r), a method for producing a graphite intercalation compound by thermal decomposition of a transition metal halide such as tungsten (W), molybdenum (Mo), and technetium (Tc) (JP-A-61-2268).
08) was proposed earlier. However, in this vapor phase pyrolysis method, the temperature at which graphite raw material is decomposed, the temperature at which graphite is deposited on a substrate, the temperature at which organometallic or transition metal halides are pyrolyzed, and the respective metals generated by decomposition The temperature at which the atoms are inserted is equal. That is, in the conventional simultaneous synthesis, the entire process was performed at one temperature at which the raw material gas for graphite was thermally decomposed.

[0005] The method for producing a graphite intercalation compound includes the following.
Solvent method, electrochemical method, mixed method
Various legal species have been reported using legal and pressurized methods.
I have. Insertion species known so far include: 1) Li, Na,
Alkali metals such as K, Rb and Cs, 2) Mg, Ca, S
alkaline earth metals such as r, 3) halogens such as chlorine and bromine
Gases, 4) halogen compounds such as ICl, 5) SbCl
_Five, SbF_Five, AlCl_Three, FeCl_Three, CuCl_Twoetc
Metal halide, 6) nitric acid, sulfuric acid, AsF _FiveEtc. acid
And 7) metals such as alkali metal-mercury and mercury-bismuth
About 300 kinds of intermetallic compounds etc. (Advances in
Physics, 30. 139 (1981)).

However, when viewed as a thermoelectric conversion material, none of the above graphite intercalation compounds was satisfactory.

[0007]

According to the present invention, a ter is provided.
(Te), bismuth (Bi), germanium (G
e), silicon (Si) and their oxides, iron (F
e) oxides and copper (Cu) oxides
The insertion species is a graphite structure every other layer or every other layer
Graphite-structured charcoal characterized by being regularly inserted in
Abstract: Provided are an elementary intercalation compound and a thermoelectric conversion element containing the same . Further, according to the present invention, the graphite structure carbon layer
A method for producing an intermetallic compound, the method comprising:
Solution area A, product deposition area B with substrate, and insertion
With the apparatus provided with the seed gas generation region C, the temperature of the region B
Set at least 50 ° C lower than the temperature of area A
While depositing intercalation compounds of graphite structure carbon on the substrate.
Of intercalation compound of graphite structure carbon characterized by performing
A method is provided.

According to the production method of the present invention, graphite structure carbon having a lower temperature and higher crystallinity than the conventional method can be produced. Therefore, it is possible to save energy and use a substrate having a relatively low temperature resistance. In addition, the manufacturing method of the present invention is 150 μV /
It becomes possible to produce an intercalation compound of graphite structure carbon having a thermoelectric power of K or more, for example, a compound having selenium, tellurium, germanium, an oxide of iron, an oxide of copper, or the like between layers. In addition, such an interlayer compound is excellent as a thermoelectric conversion material.

As the apparatus used in the method of the present invention, basically known apparatuses can be used. However, a hydrocarbon compound gas decomposition region A and a product deposition region B provided with a substrate
Need to have a configuration that can be independently controlled to each desired temperature, at least when provided in the same decomposition apparatus. The basic structure of the apparatus used in the method of the present invention is shown in FIG.

In FIG. 1, reference numeral 1 denotes a graphite raw material container containing an aliphatic hydrocarbon, an aromatic hydrocarbon, an alicyclic hydrocarbon, and the like. Reference numeral 2 denotes an insertion seed material container serving as a supply source of the insertion seed containing the insertion seed material. Reference numeral 3 denotes a reaction tube, and reference numeral 8 denotes a raw material transfer tube for transferring the raw material gas to the reaction tube 3. The gas from the graphite raw material container and the gas from the inserted seed raw material container are mixed in the middle of the transfer pipe 8, and the inserted seed raw material and the graphite raw material are simultaneously supplied to the reaction tube 3. 4 is a high-temperature side heating furnace, 5 is a low-temperature side heating furnace,
Both heat the high temperature chamber and the low temperature chamber of the reaction tube 3 respectively. The high-temperature side heating furnace 4 becomes a graphite raw material introduced from the graphite raw material container into the high-temperature chamber of the reaction tube 3, and thermally decomposes a raw material gas such as an aliphatic hydrocarbon, an aromatic hydrocarbon, or an alicyclic hydrocarbon.

The raw material gas transferred to the low-temperature chamber is deposited as graphite on the deposition-forming substrate 6 placed on the substrate holding table 7, and at this time, the inserted seed gas transferred at the same time is a graphite growth process. Is inserted between graphite layers. The remainder of the steam introduced into the reaction tube 3 is discharged through the exhaust pipe 9.
The apparatus of FIGS. 2 and 3 is a modification of the apparatus of FIG. 1 described above, and will be described in an embodiment described later.

The apparatus shown in FIGS. 1 to 3 each correspond to a high-temperature side heating furnace corresponding to a hydrocarbon compound gas decomposition region A and a product deposition region B provided with a substrate in one heating furnace. A low-temperature side heating furnace is provided. However, the high-temperature heating furnace and low-temperature heating furnace are independent heating furnaces,
A configuration in which the pipes are connected by a gas phase transfer pipe can be employed.

Further, the generation region C of the inserted seed gas is shown in FIG.
3 are the same as the decomposition area A. However, in some cases, the low-temperature heating furnace may be connected to the low-temperature heating furnace by using the low-temperature heating furnace as the generation region C. Further, the generation region C may be provided independently. The preparation of intercalation compounds of graphite structure-carbon of the present invention, the hydrocarbon compound gas is used as the main raw material.

The hydrocarbon compound may be any compound which easily becomes gaseous and is decomposed to generate carbon. Various hydrocarbon compounds known in the art can be used. For example, the hydrocarbon compound is an aliphatic or aromatic hydrocarbon,
And heterocyclic compounds. These may partially have a substituent (halogen atom, hydroxyl group, sulfonic group, nitro group, nitroso group, amino group, carboxyl group, etc.).

More specifically, saturated aliphatic hydrocarbons such as methane, ethane, propane, butane, pentane, hexane and cyclohexane; unsaturated fatty acids such as ethylene, dichloroethylene, dibromoethylene, 2-butyne, acetylene and diphenylacetylene; Group hydrocarbons: naphthalene, anthracene, pyrene, benzene, toluene, allylbenzene, hexamethylbenzene, aniline, phenol,
Aromatic hydrocarbons such as styrene and biphenyl; pyridine,
Heterocyclic compounds such as pyrrole and thiophene are exemplified.

The use of dichloroethylene, acetylene or the like can lower the heating temperature of the substrate. The insertion species used for producing the graphite intercalation compound of the present invention is not particularly limited as long as it can form an intercalation compound. However, according to the method of the present invention, it is possible to produce an intercalation compound in which Se, Te, or the like has been inserted, in which an intercalation compound could not be obtained by the conventional method.

Inserts preferably used in the present invention
The raw materials for generating gas include the following. a) For metals such as Se, Te, Si, Bi, Ge
And these oxides (eg, SeO_Two, TeO_Two, SiO
_Two, BiO_Two, Bi_TwoO_Three, GeO, GeO_TwoEtc.), c
Logenide (Example: SeCl_Four, SeBr_Four, SeI_Four,
TeCl_Four, TeBr_Four, TeI_Four, SiCl_Four, Si
Br_Four, BiCl_Four, BiBr_Four, BiI_Four, GeCl
_Four, GeBr_Four, GeI_FourEtc.); organic compounds (eg, (C
₆H_Five) _TwoSe_Two, (C₆H_Five) SeCl, C₈H₇N
Se, C₆H_FiveSeH, SeC (NH_Two)_Two, Si (O
CH_Three)_Four, Si (OC_TwoH_Five)_Four, SiH_Four, (C₆
H _Five)_ThreeSiH, (C₆H_Five)_ThreeSiCl, (CH_Three)
_ThreeSiCl, (CH_Three)_ThreeSiBr, (C_TwoH_Five)_ThreeS
iCl, (CH_Three)_FourSi, Si_TwoH₆, (C₆H _Five)
_ThreeBi, GH_FourB) Fe or Cu or an oxide thereof (eg, Fe
O, Fe_ThreeO_Four, Fe_TwoO_Three, CuO, Cu_TwoO etc.).
Other decomposition, Fe or Cu or their acids
Raw materials capable of forming a compound can also be used.

In the method of the present invention, the temperature of the hydrocarbon compound gas decomposition region A and the temperature of the product deposition region B provided with the substrate are set to be different. The temperature of the region B is at least 50 ° C. higher than the temperature of the region A, preferably 100 ° C.
Set lower than ℃. The temperatures of these two regions are set according to the type of the hydrocarbon compound gas as the raw material and the type of the raw material of the insertion seed gas.

The temperature of the area A in the preparation of an intercalation compound of graphite structure-carbon is preferably generally about 300 ° C. to 1600 ° C. is about 400 to 1500 ° C.. On the other hand, the temperature in the region B is generally about 300 ° C to 1100 ° C, preferably about 350 to 1000 ° C.
° C.

However, the temperature in the region A is a temperature suitable for simultaneously decomposing the hydrocarbon compound gas and generating the insertion seed gas (region C). In a case where a region C for generating a gas from the raw material of the insertion species is separately provided and the generated insertion species gas is directly introduced into the region B, the temperature of the region C is determined in consideration of the type of the raw material of the insertion species. However, in this case, the temperature of the region B is set at least 50 ° C. lower than the temperature of the region C.

The supply amount of the inserted seed material is set to about 0.06 to 3.0 times the supply amount of the hydrocarbon compound. More preferably, it is 0.08 to 1.5 times mol. Under conditions deviating from this, the insertion seed cannot be inserted, or even if it can be inserted, the insertion seed layer is inserted dilutely every three graphite layers or more, or due to excessive insertion, it may change over time. Because the precipitation of the intercalated species occurs,
It becomes difficult to form a graphite intercalation compound in which the above-mentioned insertion species of the present invention is inserted in an appropriate amount. For example, the hydrocarbon compound used as the graphite raw material is under the following conditions: • Supply rate: 0.05 mol / hr to 1.5 mol / hr • Molecular density: 2 × 10 ²¹ molecules / l to 2.6 × 10 ²²
When the flow rate is set to 0.5 cm / min to 70 cm / min, the supply of the intercalated seed material is performed under the following conditions: The supply rate is 0.004 mol / hour to 2.3 mol /
Time ・ Molecular number density 1.6 × 10 ²⁰ molecules / l ~ 4.0 × 1
0 ²² molecules / l · flow rate of 0.5 cm / min ～70Cm / carried out preferably in minutes.

By further finely controlling the supply amount of the insertion seed material gas and the supply amount of the hydrocarbon, the intercalation between the graphite layers in which the periodicity of the insertion seed layer is controlled is determined by the number of layers of the graphite layer to be inserted. Preparation of the compound is possible. In addition, by inserting insertion species having a thermoelectric power of 150 μV / K or more at intervals of every other layer or every two layers of the graphite structure, a graphite intercalation compound having a high thermoelectric power can be obtained. .

The thermoelectric power is T e as intercalating species is 150μV / K or more, Bi, Ge or Si, or an oxide thereof, oxides of Fe, oxides of Cu, and the like.
Quartz, sapphire,
Inorganic substances such as alumina, SiC and Si, or metals such as copper, platinum, nickel and iron are used. In particular, a metal substrate is preferable because it can be used as it is because of its conductivity. Among them, a substrate made of an iron group element (iron, cobalt, nickel) or platinum containing the same further has an effect of catalyzing a thermal decomposition reaction of various hydrocarbon compounds and an effect of accelerating carbonization of carbon. Particularly remarkable and preferable.

[0024]

The present invention is based on the finding that if the temperature of the raw material gas is increased while maintaining the substrate temperature at a low temperature, the crystallinity of the graphite structure carbon deposited on the substrate is improved. The graphite raw material gas decomposed and decomposed reaches the substrate while maintaining its excited state to some extent, and the higher the temperature of the decomposition region A of the raw material gas, the better the crystallinity.

[0025] Pyrolytic graphite or pyrolytic carbon is formed in a vapor atmosphere of the intercalating species by a thermal CVD method using the intercalating material gas and a hydrocarbon or hydrocarbon compound gas as raw materials. In a method for producing an intercalated graphite compound in which an intercalated species is inserted between layers of graphite in a carbon growth process, an intercalated species having a low boiling point or a low carbide forming temperature is inserted by separating a growth furnace into a high temperature chamber and a low temperature chamber. Therefore, even on a low-temperature substrate maintained at a temperature equal to or lower than the boiling point of the insertion species, graphite can be grown in a vapor atmosphere of the insertion species. As a result, S
It has become possible to produce a graphite intercalation compound in which an insertion species having a low boiling point such as e, Te or the like, or a low carbide formation temperature such as Bi, Ge, Si or the like is inserted between graphite layers.

Further, by controlling the supply amount of the insertion seed material gas and the hydrocarbon concentration, it is possible to produce a graphite intercalation compound in which the periodicity of the insertion seed layer, that is, the interval between the insertion seed layers to be inserted, is controlled. Became. By producing a graphite intercalation compound by such a method, it has become possible to produce a thermoelectric conversion material having a large thermoelectric power.

That is, the inserted species of the present invention has a graphite structure.
It is possible to produce an intercalation compound of graphite-structured carbon having a thermoelectric power of 150 μV / K or more, which is inserted regularly in every other layer or every two layers. The intercalation compound of the present invention has been made by finding an intercalated species arrangement that minimizes the interstitial thermal conductivity Kph and finding that the thermoelectric power α of the intercalated compound exhibits almost the same value as α of the intercalated species.

The mechanism by which this phenomenon occurs is not clear,
It is considered as follows. That is, when an insertion seed layer, which is a heteroatom layer, is inserted between the graphite layers, phonon scattering in the layer direction is amplified. This amplification effect is further increased with the increase in the insertion seed layer.
It is maximum when inserted every other layer or every other layer,
Kph becomes almost 0.

Further, when a heteroatom layer is inserted between graphite layers, charge transfer usually occurs between the nearest insertion seed layer and the graphite layer. At this time, the insertion seed layer inserted between the graphite layers is stabilized by being kept in the same ionic state as before insertion. On the other hand, the number of carriers also changes in the graphite layer due to charge transfer. At this time, the thermoelectric power α of the graphite layer changes with a change in the number of carriers. However, originally the thermoelectric power of graphite α1
^- very small at about 3MyuV, the amount of change is also very small. After all, even if the carrier-concentration changes due to charge transfer, the amount of change in the thermoelectric power α of the graphite matrix is so small that it can be neglected. Seemingly has no effect. On the other hand, the thermoelectric power of the insertion seed layer inserted between the layers of the graphite layer shows the same thermoelectric power value as the thermoelectric power α before the insertion because the insertion seed layer itself is in a state similar to that before the insertion. .

As a result, the thermoelectric power α of the intercalation compound reflects only the α of the intercalated species and becomes almost the same value as the α of the intercalated species. In the following examples, the composition and structure of the deposit were evaluated by X-ray imaging of the inserted species with an electron microscope and analysis of diffraction peaks by X-ray diffraction. The electrical conductivity was measured by a DC four-terminal method, the thermal conductivity was measured by an optical AC method using a commercially available device, and the thermoelectric power was measured by the method shown in FIG.

[0031]

EXAMPLES Example 1 and Comparative Example 1 (Reference Example) Using the apparatus shown in FIG.
Graphite structure carbon was formed using a Ni substrate as a substrate.
Table 1 shows the conditions for the formation. FIG. 5 shows the interplanar spacing and the substrate temperature dependency of the obtained product, and FIG.
Shown in

It can be seen that this embodiment has better crystallinity of the carbon film deposited on the substrate at the same temperature. In particular, the difference is remarkable in the region of the substrate temperature of about 500 to 700 ° C., which is higher than the conventional temperature of about 3.85 to 4.0 ° in this embodiment.
3.6 to 3.65 at 000 ° C, 3.5 to 1200 ° C
A surface spacing in the C-axis direction of 3.6 ° is obtained.

[0033]

[Table 1]

Examples 2-3 and Comparative Examples 2-3 (Reference
Example) Using the apparatus shown in FIG. 1, graphite-structured carbon was formed using benzene or propane as a source gas and a Ni substrate as a substrate. Table 2 shows the conditions for the formation. Table 3 shows the interplanar spacing and substrate temperature dependence of the obtained product. Compared with the conventional method in Table 3, it can be seen that towards the present embodiment is good crystallinity of the carbon film deposited on the substrate at the same temperature.
In particular, the difference is remarkable in a region where the substrate temperature is about 500 to 700 ° C.

Table 3 shows that the propane method improves the crystallinity more than benzene.

[0036]

[Table 2]

[0037]

[Table 3]

Example 4 The process of inserting tellurium atoms between layers of graphite using benzene as a hydrocarbon compound as a graphite raw material and tellurium as an insertion seed raw material is described with reference to FIG. Will be explained. Argon gas is supplied from an argon gas control system 20 into a bubble container 11 containing benzene that has been purified by vacuum distillation as a graphite raw material, and benzene is bubbled.
Feed benzene molecules to 3. At this time, the bubble container 11
The temperature of the liquid benzene therein was kept constant, and the flow rate of the argon gas was adjusted by the first valve 21 to control the supply amount of benzene molecules into the quartz reaction tube 13. Tellurium is mixed from the container 12 containing tellurium in the middle of the transfer tube 18, and benzene molecules and tellurium atoms are simultaneously supplied to the reaction tube 13. At this time, the container 12 and the transfer pipe 18 are covered with a heating tape, and by heating this to a constant temperature, tellurium inside the container 12 is evaporated, and by adjusting the second valve 22, tellurium vapor is generated at a constant speed. Transfer to reaction tube 13. On the other hand, an argon gas is supplied from the dilution line 23 to optimize the number density and the flow rate of benzene molecules and tellurium atoms in the argon gas supplied to the quartz reaction tube 13.
The reaction tube 13 is inserted into the heating furnace,
4. The low-temperature side heating furnace 15 is heated to each reaction temperature, and a holding table 17 on which a deposition generating substrate 16 for growing a graphite intercalation compound is placed is arranged in a low-temperature room of the low-temperature side heating furnace part of the reaction tube 13. Have been. The benzene molecules introduced into the reaction tube 13 are thermally decomposed in the high-temperature side heating furnace 14, and graphite or carbon deposits grow on the substrate in the low-temperature chamber. At this time, the tellurium atoms introduced at the same time are inserted as tellurium atoms between the layers of graphite during the growth process of graphite, and the resulting graphite deposit becomes a graphite intercalation compound in which tellurium atoms are inserted between the layers of the graphite layer. Become. The remainder of the steam introduced into the reaction tube 13 is discharged to the outside via the exhaust pipe 19.

In the above process, a nickel base is used for the substrate 16 for deposition generation, the temperature of the high-temperature heating furnace 14 is 1000 ° C., the temperature of the low-temperature heating furnace 15 is 750 ° C., and the tellurium evaporation temperature is 500 ° C. , Benzene and tellurium feed rates of 0.50 mol / hr and 0.38 mol / h, respectively.
As r, a graphite intercalation compound having tellurium inserted between graphite layers was obtained.

The feed rate ratio between tellurium and a hydrocarbon compound suitable for synthesizing a graphite intercalation compound in which tellurium is inserted every other layer between graphite layers varies depending on the type of hydrocarbon compound used as a raw material. However, when benzene is used as the hydrocarbon compound, the high-temperature side heating furnace temperature 100
At 0 ° C., benzene is added in an amount of 0.6 to 2.
It is effective to make the molar ratio 5 times. Further, when the amount of tellurium introduced into the reaction tube 13 is changed, the number density of tellurium atoms also changes, so that it is possible to control how many layers of the tellurium atom layer are inserted in the graphite layer. The feed rate ratio between tellurium and benzene suitable for synthesizing a graphite intercalation compound in which tellurium is inserted between every two layers of graphite is 2.5 to 5.0 times the molar ratio of benzene to tellurium 1. It is effective to do. By increasing the ratio of benzene, it is possible to insert the tellurium layer more dilutely than every third or fourth graphite layer. However, if the amount is less than this, tellurium is precipitated with time due to excessive insertion of tellurium.

The presence of tellurium atoms between the layers was confirmed by taking an X-ray image of the tellurium atoms in the graphite film with an electron microscope, whereby the tellurium atoms were uniformly present between the layers. Further, according to X-ray diffraction, reflection corresponding to the sum of the atomic radius of tellurium and the interlayer distance of graphite could be observed. In addition, it was confirmed by the same method that the interlayer compound thus obtained did not change even when its stage structure was left at a high temperature in the air.

The obtained tellurium atoms are inserted between the graphite layers.
In the direction of lamination (perpendicular to the layer) of the graphite intercalation compound
Thermoelectric power is α = 800μVK^-1Met. This value is
Antimony pentachloride, the highest value of graphite intercalation compounds
(SbCl_Five) Graphite layer obtained by inserting molecule itself
Α of inter-compound = 40 μVK^-1Much bigger and Bi
_TwoTe_ThreeΑ = 250μVK of conventional thermoelectric materials such as^-1Above
is there. The conductivity σ and the thermal conductivity κ are respectively σ = 1200
Ω^-1cm^-1, Κ = 6.0 × 10^-3Wcm^-1K^-1And
The ratio of electrical conductivity to thermal conductivity σ / κ is Bi_TwoTe_ThreeConventional heat such as
More than four times that of electrical materials. The thermoelectric power α is shown in FIG.
The temperature difference ΔT was changed from 0.2 ° C to 0.6 ° C
And the thermoelectromotive force ΔEMF corresponding to each temperature difference
And the thermoelectric power for each temperature difference is α = ΔEMF / Δ
T was calculated and the average of these values was taken.

In the above process, similar results were obtained when other hydrocarbon compounds such as propane were used as the graphite raw material. When a hydrocarbon compound having a molecular weight of 100 or less is used, the following heating furnace conditions are used:-a high-temperature heating furnace temperature of 900C to 1600C (preferably 1000C to 1500C)-a low-temperature heating furnace temperature of 550C to 900C ( Preferably 8
(00 ° C. to 900 ° C.), the feed rate ratio between tellurium and hydrocarbon compound suitable for synthesizing a graphite intercalation compound in which tellurium is inserted every other layer between graphite layers is as follows. Preferably, the compound is about 0.4-8 moles. More preferably, it was 0.5 to 6 moles. The feed rate ratio between tellurium and a hydrocarbon compound suitable for synthesizing a graphite intercalation compound in which tellurium is inserted every two layers between graphite layers is 1% tellurium.
It is effective to make the molar ratio of the hydrocarbon compound 6.0 to 12.0 times.

In this step, another inert gas such as nitrogen or helium can be used instead of the argon gas. It is also possible to use HCl gas to transport tellurium.

Example 5 Instead of tellurium used as an insertion seed material in the production method of Example 4 above, an organic metal or halide of tellurium was introduced into a reaction tube simultaneously with benzene as an insertion seed material, and obtained by thermal decomposition. Similar results were obtained by transferring the tellurium atom-inserted species to a low-temperature chamber. Hereinafter, diethyl tellurium (Te (C ₂ H ₅ ) ₂ ) was used as an insertion seed material,
A description will be given in accordance with the manufacturing process of FIG. 3 which shows the schematic diagram of FIG. 1 in more detail. That is, the argon gas control system 40 is provided in each of the first valve container 31 containing benzene subjected to the purification operation by vacuum distillation and the second valve container 32 containing diethyl tellurium subjected to the purification operation.
To supply benzene molecules and diethyl tellurium to the quartz reaction tube 33 via the transfer tube 38. On this occasion,
The temperature of the liquid benzene in the first valve container 31 and the temperature of diethyl tellurium in the second bubble container 32 are kept constant, and the flow rate of the argon gas is adjusted by the first valve 41 and the second valve 42 so that the benzene molecule and the diethyl tellurium are adjusted. The supply amount of the molecules into the quartz reaction tube 33 is controlled independently. On the other hand, an argon gas is supplied from the dilution line 43 to optimize the molecular number density and the flow rate of benzene and diethyl tellurium in the argon gas supplied to the quartz reaction tube 33.

In the above process, a nickel base material is used for the substrate 36 for deposition generation, and the temperature of the high-temperature heating furnace temperature 34 is 1100 ° C. and the temperature of the low-temperature heating furnace temperature 35 is 800
The graphite intercalation compound into which tellurium was inserted was obtained at a temperature of 0.30 mol / hr and a supply rate of benzene and diethyl tellurium of 0.30 mol / hr and 0.20 mol / hr, respectively. The feed rate ratio between diethyl tellurium and a hydrocarbon compound suitable for synthesizing a graphite intercalation compound in which tellurium is inserted every other layer between graphite layers varies depending on the type of hydrocarbon compound used as a raw material, When benzene is used as the hydrocarbon compound, it is effective to make benzene 0.5 to 2.0 times the molar amount of diethyl telluride at a high-temperature side heating furnace temperature of 1100 ° C. Further, when the amount of diethyl tellurium introduced into the reaction tube 33 is changed, the number density of tellurium atoms generated by thermal decomposition also changes, so that the number of layers of the tellurium atom layer to be inserted into the graphite layer is controlled. Is also possible. The feed rate ratio between diethyl tellurium and benzene suitable for synthesizing a graphite intercalation compound in which tellurium is inserted between every two layers of graphite is between 1.6 and 3.2 with respect to 1 diethyl tellurium. It is effective to double the molar ratio.
By increasing the proportion of benzene, it is possible to insert the tellurium layer more dilutely than every three or four graphite layers. However, below this, tellurium precipitates over time due to excessive insertion of tellurium.

The deposit was evaluated by the same method as in Example 4, and as a result, the same characteristics as in Example 4 were obtained. In the above process, similar results were obtained even when other hydrocarbon compounds such as propane were used as a graphite raw material. When a hydrocarbon compound having a molecular weight of 100 or less is used, the following heating furnace conditions are used:-a high-temperature heating furnace temperature of 900C to 1600C (preferably 1000C to 1500C)-a low-temperature heating furnace temperature of 550C to 900C ( Preferably 8
(00 ° C. to 900 ° C.), the feed rate ratio between diethyl tellurium and a hydrocarbon compound suitable for synthesizing a graphite intercalation compound in which tellurium is inserted every other layer between graphite layers is as follows: It is effective to make the hydrocarbon compound 0.5 to 5.0 moles. The feed rate ratio between diethyl tellurium and a hydrocarbon compound suitable for synthesizing a graphite intercalation compound in which tellurium is inserted between every two layers between graphite layers is as follows.
It is effective to make the amount of the hydrocarbon compound 5.0 to 12 times mol.

When the temperature on the low temperature side is 850 ° C.,
The insertion amount was the largest, and was surely inserted. This was the same in Example 4. Similar results were obtained by using tellurium hydride (TeH) instead of diethyl tellurium (Te (C ₂ H ₅ ) ₂ ) used as the seed material for insertion in this step.

Example 6 (Reference Example) Using the apparatus shown in FIG. 2, benzene was used as a hydrocarbon compound as a graphite raw material, selenium was used as an insertion seed raw material, and a nickel base was used as a substrate for deposit formation. In the same manner, a graphite intercalation compound having selenium atoms inserted between the graphite layers was produced.

In this embodiment, the temperature of the high-temperature side heating furnace is 900 ° C., the temperature of the low-temperature side heating furnace is 550 ° C., the evaporation temperature of selenium is 400 ° C., and the supply rates of benzene and selenium are 0.65 mol / hr and 0, respectively. A graphite intercalation compound into which selenium was inserted at a concentration of .70 mol / hr was obtained. The feed rate ratio between selenium and a hydrocarbon compound suitable for synthesizing a graphite intercalation compound in which selenium is inserted every other layer between graphite layers varies depending on the type of hydrocarbon compound used as a raw material. When benzene is used as the hydrogen compound, selenium 1
It is effective to make benzene 1.2 to 2.4 times the mol. The feed rate ratio of selenium and benzene suitable for synthesizing a graphite intercalation compound in which selenium is inserted between every two layers of graphite is 2.4 to 4.8 times that of selenium. Molar is effective. By increasing the ratio of benzene, it is possible to insert the selenium layer more dilutely than every three or four graphite layers. However, if it is less than this, selenium is excessively inserted, so that selenium is precipitated with time.

In the above process, similar results were obtained when other hydrocarbon compounds such as propane were used as the graphite raw material. When a hydrocarbon compound having a molecular weight of 100 or less is used, the following heating furnace conditions are used: ・ High-temperature heating furnace temperature 900 ° C to 1600 ° C (preferably 900 ° C to 1200 ° C) ・ Low-temperature heating furnace temperature 400 ° C to 700 ° C ( Preferably 4
(50 ° C. to 550 ° C.), the feed rate ratio between selenium and a hydrocarbon compound suitable for synthesizing a graphite intercalation compound in which selenium is inserted every other layer between graphite layers is as follows. It is effective to make the hydrogen compound 0.6 to 4.0 moles.
The feed rate ratio of selenium and hydrocarbon compound suitable for synthesizing a graphite intercalation compound in which selenium is inserted every two layers between graphite layers is such that the ratio of selenium to hydrocarbon compound to selenium is 4.0 to 4.0. It is effective to make it 12 times mol.

In this step, another inert gas such as nitrogen or helium can be used in place of the argon gas. The presence of selenium atoms between the layers was confirmed to be uniformly present between the layers by taking an X-ray image of the selenium atoms in the graphite film with an electron microscope. Furthermore, according to X-ray diffraction, reflection corresponding to the sum of the atomic radius of selenium and the interlayer distance of graphite could be observed. In addition, it was confirmed by the same method that the interlayer compound thus obtained did not change even when its stage structure was left at a high temperature in the air.

The obtained selenium atoms are inserted between the graphite layers.
In the direction of lamination (perpendicular to the layer) of the graphite intercalation compound
Thermoelectric power is α = 900μVK^-1Met. This value is
Antimony pentachloride, the highest value of graphite intercalation compounds
(SbCl_Five) Graphite layer obtained by inserting molecule itself
Α of inter-compound = 40 μVK^-1Much bigger and Bi
_TwoTe_ThreeΑ = 250μVK of conventional thermoelectric materials such as^-1Above
is there. The conductivity σ and the thermal conductivity κ are σ = 1100, respectively.
Ω^-1cm^-1, Κ = 5.5 × 10^-3Wcm^-1K^-1And
The ratio of electrical conductivity to thermal conductivity σ / κ is Bi_TwoTe_ThreeConventional heat such as
More than four times that of electrical materials.

The inserted seed material was produced by the method of Example 6 described above.
Diphenyl diselena instead of selenium
Id ((C₆H_Five)_TwoSe_Two), Phenyl / selenyl /
Chloride (((C₆H_Five) SeCl), methyl ben
Z Serenazole (C₈H₇NSe), selenopheno
Le (C₆H_FiveSeH), selenoureas (SeC (N
H _Two)_Two), Etc., as an insertion seed material,
Same as hydrocarbon compounds such as benzene and propane as graphite raw materials
Sometimes introduced into the reaction tube and obtained by thermal decomposition in a high-temperature heating furnace.
Selenium intercalated species to be transferred to a cold room
Also obtained similar results. Using the above inserted seed material,
When a hydrocarbon compound having an amount of 100 or less is used,
Heating furnace conditions: ・ High-temperature heating furnace temperature 900 ° C to 1600 ° C (preferably
900 ° C to 1200 ° C) ・ Low-temperature furnace temperature 400 ° C to 700 ° C (preferably 4 ° C)
(50 ° C. to 550 ° C.).
Preferably, the ratio is about 0.6 to 10 moles. Better
More preferably, it was 0.9 to 7 times mol.

Example 7 Using the apparatus shown in FIG. 2, in the same manner as in Examples 4 and 6, benzene was used as a hydrocarbon compound as a graphite raw material, and bismuth fluoride, selenium oxide or Using tellurium dioxide, these insertion seed materials were inserted as they were between graphite layers without being thermally decomposed at the high-temperature side heating furnace temperature. Table 4 shows one embodiment of the above-described steps, such as the evaporation temperature of the inserted seed material, the high-temperature heating furnace temperature, the low-temperature heating furnace temperature, and the gas supply conditions.

[0056]

[Table 4] In the above process, similar results were obtained even when other hydrocarbon compounds such as propane were used as a graphite raw material. When a hydrocarbon compound having a molecular weight of 100 or less is used, the following heating furnace conditions are used: ・ High-temperature heating furnace temperature 750 ° C to 1400 ° C (preferably 750 ° C to 1100 ° C) ・ Low-temperature heating furnace temperature 400 ° C to 800 ° C ( Preferably 5
(50 ° C. to 800 ° C.), the supply molar ratio of the hydrocarbon compound to the insertion seed material 1 is preferably about 0.6 to 10 times mol. More preferably, it was 0.7 to 6 times mol.

Example 8 Germanium tetrachloride, silicon tetrachloride, tellurium chloride,
Bismuth tribromide, cupric bromide, ferrous bromide, ferric bromide
To insert low-boiling-point, low-decomposition-temperature insertion species such as iron, germanium bromide, selenium bromide, silicon bromide, bismuth iodide, germanium iodide, and selenium iodide between graphite layers 2, the low-temperature-side heating furnace 15 around the low-temperature chamber for heating the substrate holder 17 of the reaction tube 13 is removed, and the substrate holder 17 is used instead. The substrate itself is directly heated by resistance heating to control the temperature of the substrate 16. Further, the inserted seed material was directly transferred to the low-temperature chamber substrate without passing through the high-temperature chamber of the reaction tube 13. Using the above apparatus, dichloroethylene which is easily pyrolyzed at a low temperature as a hydrocarbon compound as a graphite raw material, a nickel base material as a base material for deposit formation, and germanium tetrachloride, silicon tetrachloride,
Tellurium chloride, bismuth bromide, germanium bromide, 4
By using selenium bromide, silicon bromide, bismuth iodide, germanium iodide and selenium iodide,
These vapors were inserted between layers of graphite as insertion seeds as they were without decomposition. Table 5 shows one embodiment of the steps for inserting the insertion seed, such as the evaporation temperature of the insertion seed material, the high-temperature side heating furnace temperature, the substrate temperature, and the gas supply conditions.

[0058]

[Table 5] In the above step, the following heating furnace conditions:-High-temperature side heating furnace temperature 300 ° C to 800 ° C (preferably 4 ° C)
(00 ° C to 800 ° C) ・ Substrate temperature 200 ° C to 600 ° C (preferably 300 ° C to 800 ° C)
(550 ° C.), it is preferable that the supply amount of dichloroethylene is about 1.2 to 16 times mol with respect to the insertion seed material 1. More preferably, the molar amount was 1.5 to 12 times.

In the above process, similar results were obtained by using acetylene instead of dichloroethylene used as a graphite raw material.

Example 9 Iron, copper, germanium, bismuth, silicon, bismuth oxide, cuprous oxide, cupric oxide, ferrous oxide, and tertiary oxide
Implemented to insert intercalation species such as iron, ferric oxide, germanium oxide, germanium dioxide, silicon oxide, etc., between graphite layers, which easily form carbides in the presence of carbon atoms at high boiling point and high vapor pressure at high temperatures. 2, the low-temperature side heating furnace 15 around the low-temperature chamber for heating the substrate holder 17 of the reaction tube 13 was removed, and the substrate holder 17 itself was replaced with the apparatus of FIG. The temperature of the substrate 16 was controlled by direct heating by resistance heating, and the inserted seed material was transferred directly to the low-temperature chamber substrate without passing through the high-temperature chamber of the high-temperature side heating furnace section 14 of the reaction tube 13. In addition, a high frequency induction heating method capable of heating up to 2500 ° C. was used for heating for evaporating the inserted seed material. By this method, the reaction tube 13
In the high-temperature chamber inside, the intercalated species reacts at high temperature with the pyrolysis gas of the graphite raw material to form carbides, and on the low-temperature side substrate, iron, copper, germanium, bismuth, silicon,
Bismuth oxide, cuprous oxide, cupric oxide, ferrous oxide,
Ferric oxide, ferric oxide, germanium oxide, germanium dioxide, and silicon oxide could be inserted between graphite layers as insertion species. Table 6 shows one embodiment of the steps for inserting the insertion seed, such as the evaporation temperature of the insertion seed material, the high-temperature side heating furnace temperature, the substrate temperature, and the gas supply conditions.

[0061]

[Table 6] In the above process, similar results were obtained even when other hydrocarbon compounds such as propane were used as a graphite raw material. When a hydrocarbon compound having a molecular weight of 100 or less is used, the following heating furnace conditions are used: a high-temperature heating furnace temperature of 900 ° C to 1600 ° C (preferably 1000 ° C to 1500 ° C) a substrate temperature of 700 ° C to 900 ° C (preferably 800 ° C) ° C ~
(900 ° C.), the supply molar ratio of the hydrocarbon compound to the insertion seed material 1 is preferably about 0.5 to 6 moles. More preferably, it was 0.5 to 3 moles.

Example 10 In place of the inserted seed material used in the production method of Example 9 above,
The above-described example is also applicable to a method in which an organic metal or halide of germanium, bismuth, or silicon is introduced into a reaction tube at the same time as benzene as an insertion seed material, and germanium, bismuth, and silicon atoms obtained by thermal decomposition are transferred to a low temperature chamber as insertion seeds. The same results as in Example 9 were obtained.

The process of inserting bismuth between graphite layers using benzene as a hydrocarbon compound as a graphite raw material and triphenylbismuth ((C ₆ H ₅ ) ₃ Bi) as an insertion seed raw material will be described below with reference to FIG. . Argon gas is supplied from an argon gas control system 20 into a bubble container 11 containing benzene that has been purified by vacuum distillation as a graphite raw material, and benzene is bubbled. Feed benzene molecules. At this time, the temperature of the liquid benzene in the bubble container 11 was kept constant, and the flow rate of the argon gas was adjusted by the first valve 21 to control the supply amount of benzene molecules into the quartz reaction tube 13. Triphenylbismuth is mixed from the container 12 containing triphenylbismuth in the middle of the transfer tube 18, and benzene molecules and triphenylbismuth molecules are simultaneously supplied to the reaction tube 13. At this time, the container 12 and the transfer pipe 18 are covered with a heating tape, and by heating this to a constant temperature, the triphenylbismuth inside the container 12 is evaporated, and further by adjusting the second valve 22 at a constant speed. Transfer steam. On the other hand, the dilution line 23
Argon gas is further supplied to optimize the number density and flow rate of benzene molecules and triphenylbismuth molecules in the argon gas supplied to the quartz reaction tube 13. The reaction tube 13 is inserted into the heating furnace, and the high-temperature heating furnace 14 and the low-temperature heating furnace 1 are inserted.
Deposition substrates 5 are heated to the respective reaction temperatures, and in a low-temperature chamber of the reaction tube 13, a deposition generation substrate 1 for growing a graphite intercalation compound.
6 is placed. Reaction tube 13
The benzene molecules introduced therein are thermally decomposed and a graphite deposit grows and forms on the substrate in the low-temperature furnace. At this time,
The triphenylbismuth is also thermally decomposed in the high-temperature chamber, and the resulting bismuth atoms are transported to the low-temperature chamber, and the graphite obtained as a result of being inserted as a bismuth atom between the layers of the graphite deposit during the growth of the graphite deposit on the low-temperature substrate. The deposit becomes a graphite intercalation compound in which bismuth atoms are inserted between the layers of the graphite layer.

In the above process, a nickel base material was used as the substrate for deposition generation, and the temperature of the high-temperature side heating furnace was set to 1150
° C, the low-temperature side furnace temperature is 850 ° C, the evaporation temperature of triphenylbismuth is 100 ° C, and the supply rates of benzene and triphenylbismuth are 1.0 mol / hr and 0.9 mol, respectively.
A graphite intercalation compound into which bismuth was inserted was obtained as mol / hr.

The existence of bismuth atoms between the layers was confirmed by taking an X-ray image of the bismuth atoms in the graphite film with an electron microscope, whereby the bismuth atoms were uniformly present between the layers. Further, according to X-ray diffraction, reflection corresponding to the sum of the atomic radius of bismuth and the interlayer distance of graphite could be observed. The feed rate ratio between triphenylbismuth and a hydrocarbon compound suitable for synthesizing a graphite intercalation compound in which bismuth is inserted every other layer between graphite layers varies depending on the type of hydrocarbon compound used as a raw material. When benzene is used as the hydrocarbon compound, the heating furnace temperature is 1150
At ℃, it is effective to make benzene 0.5 to 1.0 times mol per 1 of triphenylbismuth. Also,
When the amount of triphenylbismuth introduced into the reaction tube 13 is changed, the number density of bismuth atoms generated by thermal decomposition also changes. Control is also possible. The feed rate ratio of triphenylbismuth and benzene suitable for synthesizing a graphite intercalation compound in which bismuth is inserted between every two layers of graphite is 1.0 to 2.0. It is effective to make the molar ratio 5 times. By increasing the ratio of benzene, the bismuth layer can be inserted as thin as three or four graphite layers or more. However, when the amount is less than this, excessive insertion of bismuth causes precipitation of bismuth with time.

The bismuth atom obtained in this way is a graphite layer.
Direction of the graphite intercalation compound inserted between layers
Α) = 150μVK^-1Met. this
The value is the conventional highest value, antimony pentachloride (SbC
l_Five) Graphite intercalation compound obtained by inserting molecule itself
Thermoelectric power α = 40μVK^-1That is all. Also the conductivity
σ and thermal conductivity κ are σ = 1900Ω respectively^-1cm^-1, Κ =
1.1 × 10^-2Wcm^-1K ^-1And electrical and thermal conductivity
Ratio σ / κ is Bi_TwoTe_Three4 times or more of conventional thermoelectric materials such as
Became.

The same result can be obtained by using bismuth trichloride or the like in addition to triphenylbismuth as a raw material for forming a graphite intercalation compound in which bismuth is inserted between graphite layers. Was done. In the above process, similar results were obtained even when other hydrocarbon compounds such as propane were used as a graphite raw material. When a hydrocarbon compound having a molecular weight of 100 or less is used, the following heating furnace conditions are used:-a high-temperature heating furnace temperature of 900C to 1600C (preferably 1000C to 1200C)-a low-temperature heating furnace temperature of 600C to 900C ( Preferably 7
(00 ° C. to 900 ° C.), the feed rate ratio between triphenylbismuth and hydrocarbon compound suitable for synthesizing a graphite intercalation compound in which bismuth is inserted every other layer between graphite layers is 1 It is effective to make the amount of the hydrocarbon compound 0.5 to 2.0 times mol. The feed rate ratio of triphenylbismuth and hydrocarbon compound suitable for synthesizing a graphite intercalation compound in which bismuth is inserted every other layer between graphite layers is as follows. It is effective to make it 0-5.0 times mol.

In this step, argon gas was used.
Use other inert gas instead, such as nitrogen, helium, etc.
it can. In the above process, tetramethoxy sila
(Si (OCH_Three)_Four), Tetraethoxysilane
(Si (OC_TwoH_Five)_Four), Silane (SiH_Four),bird
Phenyl silane ((C₆H_Five)_ThreeSiH), Trife
Nyl chlorosilane ((C ₆H_Five)_ThreeSiCl), bird
Methylchlorosilane ((CH_Three)_ThreeSiCl), trim
Cyl bromosilane ((CH_Three)_ThreeSiBr), Trier
Chill silane ((C _TwoH_Five)_ThreeSiH), triethyl
Chlorosilane ((C_TwoH_Five)_ThreeSiCl), tetramethyl
Lusilane ((CH_Three)_FourSi), disilane (Si
_TwoH₆) Is used as an insertion seed material,
Recon atoms could be inserted between graphite layers. Ma
In addition, germane (GeH_Four), Etc.
Using a metal compound to control the insertion of the germanium element
It could be inserted between graphite layers.

In the above process, as a graphite raw material,
Similar results were obtained using other hydrocarbon compounds such as propane. When a hydrocarbon compound having a molecular weight of 100 or less is used, the following heating furnace conditions are used:-a high-temperature heating furnace temperature of 900C to 1600C (preferably 1000C to 1300C)-a low-temperature heating furnace temperature of 600C to 900C ( Preferably 8
(00 ° C. to 900 ° C.), the supply molar ratio of the hydrocarbon compound to the insertion seed material 1 is preferably about 0.5 to 7 times mol. More preferably, it was 0.5 to 4 moles.

Comparative Example 4 Conventionally, various methods have been developed as a method for inserting an insertion species between graphite layers in order to form a graphite intercalation compound, and graphite having various insertion species inserted by these methods has been developed. Interlayer compounds have been created. As the insertion method, for example, as described in “Carbon”, Vol. 111, p. 171 (1982) published by the Society of Carbon Materials, Japan, 1) gas phase reaction method (two-bulb method), 2) solvent method 3) electrochemical method,
4) Mixing method, 5) Pressurization method and the like are well known. Also,
The insertion species known so far are: 1) Li, Na, K, R
b, an alkali metal such as Cs, 2) Mg, Ca, Sr alkaline earth metals such as 3) chlorine, halogen gases such as bromine, 4) a halogen compound such as ICl, 5) SbCl _5,
Metal halides such as SbF ₅ , AlCl ₃ , FeCl ₃ , CuCl ₂ , 6) nitric acid, sulfuric acid, acids such as AsF ₅ ,
7) About 300 kinds of intermetallic compounds such as alkali metal-mercury and mercury-bismuth (Advances in Physiology)
cs, 30, 139 (1981)). Is the Se, T according to the present invention.
There is no example in which an oxide of e, Bi, Ge, Si, or Fe, Cu is used as an insertion species. Attempts were made to insert these insertion species according to the present invention by the above-mentioned conventional method, but they could not be inserted.

Comparative Example 5 The gas phase reaction method (two-bulb method) of the above 1) described in Comparative Example 4
With the discovery of various catalysts, the number of insertion species that can be inserted between layers of graphite is increasing. For example, it has been reported that chlorides such as SiCl _4, which had been reported not to be inserted, could be inserted by using chlorine gas as a catalyst, or that fluorine has conventionally been covalently bonded to carbon and has been reacted with graphite. AgF, W, where only fluorinated graphite was obtained
It has been reported that when F ₆ and SbF ₅ were used as a catalyst, a graphite intercalation compound into which fluorine was inserted was obtained. Even if chlorine gas, AgF, WF ₆ , SbF _5, or the like was used as a catalyst using the method 1), the insertion species according to the present invention could not be inserted.

Comparative Example 6 As a very specific example, many scientists
Although reconsideration has not reached a firm conclusion, there have been reports of reports on the formation of graphite intercalation compounds into which the following insertion species have been inserted. Tetrahydrofuran (TH
In F), a graphite intercalation compound of potassium is reacted with a transition metal salt to obtain Ti, Mn, Fe, Co, C
It has been reported that a graphite intercalation compound having u and Zn inserted therein was obtained (Journal of Chemical Society, Dalton Transa
ction, 12, 2026-2028 (1979)). A molded body of a mixture of lanthanoid metal powder and graphite is heated and solid
There is also a report that a graphite intercalation compound into which lanthanoids such as m, Eu, Tm, and Yb were inserted was obtained (Carbon, 18,
203-209 (1980)). Also Journal of the American Chem
ical Society, 97, 3366-3373 (1975)) includes Fe, C
It is reported that a graphite intercalation compound having these transition metals inserted therein was obtained by reducing chlorides of o, Ni, Mn, Cu, and Mo. Even with these methods, it was not possible to insert the oxide of Se, Te, Bi, Ge, Si or Fe, Cu according to the present invention.

[0073]

According to the method of the present invention, high-quality graphite-structured carbon having high crystallinity can be obtained at a lower substrate temperature than before, and a new graphite intercalation compound which cannot be obtained by the conventional method can be obtained. Provided. Further, the graphite intercalation compound of the present invention has a large thermoelectric power, so that a high-performance thermoelectric conversion element can be manufactured.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing a manufacturing apparatus used in an embodiment of the present invention.

FIG. 2 is a diagram showing details of a manufacturing apparatus used in an embodiment of the present invention.

FIG. 3 is a diagram showing details of a manufacturing apparatus used in an embodiment of the present invention.

FIG. 4 is a schematic diagram of a thermoelectric power measuring device.

FIG. 5 is a view showing the relationship between the surface spacing of graphite structure carbon and the substrate temperature in Example 1.

FIG. 6 is a graph showing the relationship between the surface spacing of graphite structure carbon of Comparative Example 1 and the substrate temperature.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Graphite raw material container 2 Insert seed raw material container 3 Reaction tube 4 High-temperature side heating furnace 5 Low-temperature side heating furnace 6 Substrate 7 Substrate holding stand 8 Raw material transfer pipe 9 Exhaust pipe 10 Heater 11 Graphite raw material bubble container 12 Insert seed raw material container 13 Quartz reaction Pipe 14 High-temperature heating furnace 15 Low-temperature heating furnace 16 Deposition substrate 17 Substrate holder 18 Raw material transfer pipe 19 Exhaust pipe 20 Argon gas control system 21 First valve 22 Second valve 23 Dilution line 31 First bubble container 32 First 2 bubble container 33 Quartz reaction tube 34 High-temperature side heating furnace 35 Low-temperature side heating furnace 36 Substrate for deposition generation 37 Substrate holder 38 Raw material transfer pipe 39 Exhaust pipe 40 Argon gas control system 41 First valve 42 Second valve 43 Dilution line 51 Sample 52 Copper high-temperature heat reservoir 53 Copper low-temperature heat reservoir 54 Heater 55 Heater 56 PID control system 5 Temperature difference control thermocouple 58 thermoelectromotive force measurement μV meter 59 temperature difference thermocouples 60 Temperature difference measurement μV meter 61 temperature measuring thermocouple 62 exhaust system for measurement

Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI C01B 31/04 102 C01B 31/04 102 (72) Inventor Shigeo Nakajima 22-22 Nagaikecho, Abeno-ku, Osaka-shi, Osaka Sharp Corporation (56) References JP-A-63-206472 (JP, A) JP-A-62-226808 (JP, A) JP-A-61-223179 (JP, A) JP-A-61-222183 (JP, A) -43607 (JP, B1) JP 46-43606 (JP, B1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C01B 31/00 C01B 31/04 101 C01B 31/04 102 C23C 16 / 26 H01L 35/22 H01L 35/34

Claims (7)

(57) [Claims] (1) tellurium (Te), bismuth (Bi),
Rumanium (Ge), silicon (Si) and their
Oxides, oxides of iron (Fe) and oxides of copper (Cu)
And wherein the intercalating species to be selected, every other layer of the graphite structure, or to become inserted regularly with a period of 2 every other layer from
Intercalation compound of the graphite structure carbon. 2. Tellurium (Te), bismuth (Bi),
Rumanium (Ge), silicon (Si) and their
Oxides, oxides of iron (Fe) and oxides of copper (Cu)
Insertion species selected from every other layer of graphite structure, or
Graphite-structured carbon that is regularly inserted every two layers
Thermoelectric conversion element containing an intercalation compound. 3. Interlayer formation of the graphite structure carbon according to claim 1.
A method of manufacturing a compound, decomposition area A of a hydrocarbon compound gas, product deposition region B having a substrate, the apparatus provided with the generating region C of and inserted species gas, the temperature of the region B while set to at least 50 ° C. than the lower have a temperature above the temperature of the area a, a manufacturing method of intercalation compound of graphite structure-carbon which is characterized in that the deposition on the substrate of the intercalation compound of graphite structure-carbon. Wherein the temperature of the realm A is 300 ° C. to 1600 ° C.
Wherein the temperature of the region B is 300 ° C. to 1100 ° C.
3. The manufacturing method of 3 . 5. The temperature of the realm A is 400 ° C. to 1500 ° C.
Wherein the temperature of the region B is 350 ° C. to 1000 ° C.
4. The manufacturing method of 4 . 6. Insert species gas generating material Gath Lulu (T
e), bismuth (Bi), germanium (Ge) or silicon (Si), or method of claim 3 is these halides or organic compounds. 7. generating material is iron inserts species gas (Fe) or copper (Cu), or an oxide thereof according to claim 3
Manufacturing method.