# Patent

## Title
P-type semiconductor composed of magnesium, silicon, tin, and germanium, and method for manufacturing the same

## Abstract

A manufacturing method for a p-type semiconductor formed by sintering a compound represented by the general chemical formula: Mg2SiXSnYGeZ (where X+Y+Z=1, X>0, and Y>0, Z>0). The p-type semiconductor has a composition in which X is in the range of 0.00<X≦0.25, and Z satisfies the relationship: −1.00X+0.40≧Z≧−2.00X+0.10, where Z>0.00, and Y is in the range of 0.60≦Y≦0.95, and Z satisfies either of the relationships: −1.00Y+1.00≧Z≧−1.00Y+0.75, where 0.60≦Y≦0.90 and Z>0.00, and −2.00Y+1.90≧Z≧−1.00Y+0.75, where 0.90≦Y≦0.95 and Z>0.00.

## Background
BACKGROUND
The present disclosure relates to a p-type semiconductor composed of magnesium, silicon, tin, and germanium, and a method for manufacturing the same.
Recently, attempts have been made to improve thermoelectric performance by reducing the resistivity by carrier concentration control by doping a Mg2Si-based material with a p-type dopant (for example, Ag, Ga, or Li). Examples of such materials include:
Mg2Si+1 at % Ag, ZT=0.1 (560 K): (See M. Akasaka et al., J. Appl. Phys., 104, 013703, 2008).
Mg2Si0.6Ge0.4+0.8% Ga, ZT=0.36 (625 K): (see H. Lhou-Mouko et al., J. Alloys Compd., 509, pp. 6503-6508, 2011).
Mg2Si0.25Sn0.75+Ag-20000 ppm and Li-5000 ppm, ZT=0.32 (600 K): (see Japanese Published Unexamined Patent Application No. 2010-37641).
SUMMARY
Mg2(SiSn) and Mg2(SiGe) have been studied as promising p-type semiconductors, however, there are no known attempts that have been developed into semiconductors on a practical level. P-type semiconductors Mg2(SiSn) and Mg2(SiGe) are solid solutions with Mg2Si, and it is believed that Ge and Sn contribute to p-type conduction in the solid solutions. Therefore, elements that can change the Si site of the base composition must form an anti-fluorite structure with Mg. Such metal elements are limited to silicon (Si), germanium (Ge), tin (Sn), and lead (Pb) of Group 14. However, Pb is generally excluded from this list of elements because it is a hazardous metal.
An attempt was made to improve the performance of a p-type thermoelectric semiconductor by using the following quaternary system:
Mg2SiXSnYGeZ, where X+Y+Z=1 and X>0, Y>0, Z>0.
When using ternary Mg2SiSn, only two phase diagrams of Mg2Si and Mg2Sn are considered. However, when using the above-mentioned quaternary system, four phase diagrams of Mg2Ge, Mg2(SiSn), Mg2(SiGe), and Mg2(SnGe) must be considered. As a result, preparation of a single-phase sample of the quaternary system is difficult. These are problems that the present disclosure is intended to solve.
In view of the circumstances described above, the present disclosure addresses the above-described problems. One embodiment according to the present disclosure provides a method for manufacturing a p-type semiconductor composed of magnesium, silicon, tin, and germanium. The method of manufacturing the p-type semiconductor involves sintering a compound represented by the following general chemical formula:
Mg2SiXSnYGeZ, where X+Y+Z=1 and X>0, Y>0, Z>0 and is obtained through liquid-solid reaction of magnesium, silicon, tin, and germanium as raw materials. The obtained semiconductor is a p-type semiconductor satisfying the following equations:
X is in the range of 0.00<X≦0.25, and Z satisfies the relationship of −1.00X+0.40≧Z≧−2.00X+0.10, where Z>0.00, and
Y is in the range of 0.60≦Y≦0.95, and Z satisfies either of the following relationships:
−1.00Y+1.00≧Z≧−1.00Y+0.75, when 0.60≦Y≦0.90 and Z>0.00, and
−2.00Y+1.90≧Z≧−1.00Y+0.75, when 0.90≦Y≦0.95 and Z>0.00.
Another embodiment according to the present disclosure provides a p-type semiconductor composed of magnesium, silicon, tin, and germanium. The p-type semiconductor is manufactured by sintering a material represented by the following general chemical formula:
Mg2SiXSnYGeZ, where X+Y+Z=1 and X>0, Y>0, Z>0 obtained through liquid-solid reaction of magnesium, silicon, tin, and germanium as raw materials.
The obtained semiconductor is a p-type semiconductor satisfying the following equations:
X is in the range of 0.00<X≦0.25, and Z satisfies the relationship:
−1.00X+0.40≧Z≧−2.00X+0.10, where Z>0.00, and
Y is in the range of 0.60≦Y≦0.95, and Z satisfies either of the following relationships:
−1.00Y+1.00≧Z≧−1.00Y+0.75, when 0.60≦Y≦0.90 and Z>0.00, and
−2.00Y+1.90≧Z≧−1.00Y+0.75, when 0.90≦Y≦0.95 and Z>0.00.
The above embodiments make it possible to easily manufacture a p-type semiconductor represented by the following general chemical formula:
Mg2SiXSnYGeZ, where X+Y+Z=1 and X>0, Y>0, Z>0.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a process chart for obtaining a p-type semiconductor according to an embodiment of the present disclosure.
FIG. 2A is a table showing compositions of weighed values of p-type semiconductors, and FIG. 2B is a table showing compositions of p-type semiconductors according to the present disclosure.
FIG. 3 is a graph showing X-ray diffraction measurement results of Mg2Si0.25SnYGeZ in various p-type semiconductors.
FIG. 4 is a table showing the compositions (weighed values) of Mg2SiXSnYGeZ and thermoelectric properties thereof at a room temperature in various p-type semiconductors.
FIG. 5A, FIG. 5B, and FIG. 5C are graphs showing the relationships between the Ge composition and the Seebeck coefficient α, the thermal conductivity κ, and the resistivity ρ in various p-type semiconductors.
FIG. 6 is a graph showing the relationship between X and Z in various p-type semiconductors.
FIG. 7 is a graph showing the relationship between Y and Z in various p-type semiconductors.



DETAILED DESCRIPTION OF THE EMBODIMENTS
The present disclosure provides a p-type semiconductor made of a sintered compact of an intermetallic compound of magnesium (Mg), silicon (Si), tin (Sn), and germanium (Ge), which is represented by the following general chemical formula:
Mg2SiXSnYGeZ, wherein X+Y+Z=1 and X>0, Y>0, Z>0. The sintered compact of the intermetallic compound is manufactured as follows.
Granular Mg and Sn with a grain size of approximately 2 to 10 mm are prepared, and powdery Si and Ge with a grain size of approximately several tens of μm are prepared. Predetermined amounts of these materials are weighed and put into a carbon board. The carbon board is covered with a carbon lid, and heated for 4 hours at an absolute temperature of 1173 K under an atmosphere of 0.1 MPa ArH2 (3 weight % hydrogen) to cause a liquid-solid reaction.
The obtained solid solution is pulverized into powder with a grain size of 38 to 75 μm, and sintered by hot-pressing. The sintering pressure is standardized to 50 MPa and the sintering time is standardized to 1 hour. The sintering temperature was determined according to each Sn composition amount Y. The sintering temperature is set to 1190 K when Y=0, 1040 K when Y=0.60 or 0.65, and 930 K when Y=0.75 or 0.90.
Weighed values (mole ratios) and compositions (mole ratios) of several sintered compacts obtained as described above are shown in the tables of FIG. 2. According to this, the weighed values (FIG. 2A) and the compositions (FIG. 2B) of the sintered compacts are found to have changed little when comparing the amounts of the Mg, Si, Sn and Ge before and after sintering.
Further, in FIG. 3, results of X-ray diffraction measurement of Mg2Si0.25SnYGeZ obtained as described above are shown. According to X-ray diffraction, peaks were observed with all of the sintered compacts existing between Mg2Si and Mg2Sn having an anti-fluorite structure. Only peaks caused by the anti-fluorite structure were observed, and no peaks were observed with oxides, Mg2Si, Mg2Ge, and Mg2Sn. Based on the data in FIG. 3, it was confirmed that all of the sintered compacts were single-phase. The same results were obtained with other sintered compacts.
Next, the conduction types, the Seebeck coefficients α (μV/K), the thermal conductivities κ (W/mK), and the resistivities ρ (Ωm) of various sintered compacts of Mg2SiXSnYGeZ thus obtained are shown in the table of FIG. 4. In FIG. 5, graphs showing the relationships between the Ge composition and the Seebeck coefficient α, the thermal conductivity κ, and the resistivity ρ are shown.
Next, conduction types of semiconductors with variable values for X and Z based on the results of FIG. 4 are plotted in FIG. 6. Conduction types of these semiconductors in which the values between Y and Z change are plotted in FIG. 7. From these graphs, the conduction type border between the p-type and the n-type is found to have changed linearly. In each graph, ∘ indicates p-type, and x indicates n-type.
First, observing the relationship between X and Z in FIG. 6, as a p-type semiconductor, X is in the range of 0.00<X≦0.25. When X is in this range, a maximum value Zmax and a minimum value Zmin of Z for obtaining a p-type semiconductor change linearly in relation to X. A linear function of Zmax and a linear function of Zmin are respectively obtained as follows:
Zmax=−1.00X+0.40
Zmin=−2.00X+0.10, where Zmin>0.00.
It is confirmed that, as a p-type semiconductor, X and Z fall within the shaded range shown in FIG. 6, that is, X and Z satisfy the following relationship:
−1.00X+0.40≧Z≧−2.00X+0.10, where Z>0.00.
Observing the relationship between Y and Z in FIG. 7, as a p-type semiconductor, Y is in the range of 0.60≦Y≦0.95. When Y is in this range, a maximum value Zmax and a minimum value Zmin of Z for obtaining a p-type semiconductor change linearly in relation to Y, and a linear function of Zmax and a linear function of Zmin are obtained as follows:
Zmax=−1.00Y+1.00, where 0.60≦Y≦0.90
Zmax=−2.00Y+1.90, where 0.90≦Y≦0.95
Zmin=−1.00Y+0.75, where Zmin>0.00.
It is confirmed that as a p-type semiconductor, Y and Z fall within the shaded range shown in FIG. 7, that is, Y and Z satisfy the following relationship:
−1.00Y+1.00≧Z≧−1.00Y+0.75, where 0.60≦Y≦0.90 and Z>0.00, or
−2.00Y+1.90≧Z≧−1.00Y+0.75, where 0.90≦Y≦0.95 and Z>0.00.
The present disclosure is applicable to obtaining of a p-type semiconductor composed of Mg2SiXSnYGeZ.

## Claims

1. A method for manufacturing a p-type semiconductor composed of magnesium, silicon, tin, and germanium comprising:
mixing magnesium, silicon, tin, and germanium as raw materials,
obtaining, by liquid-solid reaction, a solid solution of the magnesium, silicon, tin, and germanium mixture represented by the following general chemical formula:
Mg2SiXSnYGeZ, where X+Y+Z=1 and X>0, Y>0, Z>0, and
sintering the obtained mixture to produce a p-type semiconductor, the p-type semiconductor represented by the following general chemical formula:
Mg2SiXSnYGeZ, wherein:
X is in the range of 0.00<X≦0.25, and Z satisfies the relationship of −1.00X+0.40≧Z≧−2.00X+0.10, and Z>0.00, and
Y is in the range of 0.60≦Y≦0.95, and Z satisfies either of the following relationships:
−1.00Y+1.00≧Z≧−1.00Y+0.75, where 0.60≦Y≦0.90 and Z>0.00, and
−2.00Y+1.90≧Z≧−1.00Y+0.75, where 0.90≦Y≦0.95 and Z>0.00.

2. The method according to claim 1, wherein Y is in the range of 0.65≦Y≦0.90.

3. A p-type semiconductor composed of magnesium, silicon, tin, and germanium, wherein:
the p-type semiconductor is manufactured by a liquid-solid reaction of magnesium, silicon, tin, and germanium as raw materials to obtain a material represented by the following general chemical formula:
Mg2SiXSnYGeZ, where X+Y+Z=1 and X>0, Y>0, Z>0, followed by sintering to obtain a the p-type semiconductor, the p-type semiconductor represented by the following general chemical formula:
Mg2SiXSnYGeZ, where:
X is in the range of 0.00<X≦0.25, and Z satisfies the relationship:
−1.00X+0.40≧Z≧−2.00X+0.10, where Z>0.00, and
Y is in the range of 0.60≦Y≦0.95, and Z satisfies either of the following relationships:
−1.00Y+1.00≧Z≧−1.00Y+0.75, where 0.60≦Y≦0.90 and Z>0.00, and
−2.00Y+1.90≧Z≧−1.00Y+0.75, where 0.90≦Y≦0.95 and Z>0.00.

4. The p-type semiconductor of claim 3, wherein Y is in the range of 0.65≦Y≦0.90.