# US 8,772,622 B2 · Doped tin tellurides for thermoelectric applications

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- Number: US 8,772,622 B2
- Document ID: US8772622B2
- Status: Granted
- Kind: B2
- Application number: 12/866,552
- Filed: 2009-02-05
- Published: 2011-01-20
- Granted: 2014-07-08
- Earliest claimed: 2008-02-07
- Assignees: BASF SE
- Applicants: Frank Haass
- Inventors: Frank Haass
- Web page: https://patentgrep.com/patent/US8772622B2

## CPC

- C01B 19/002: {Compounds containing, besides selenium or tellurium, more than one other element, with -O- and -OH not being considered as anions}
- C01B 19/007: {Tellurides or selenides of metals (C01B19/002 takes precedence)}
- H10N 10/01: Manufacture or treatment
- H10N 10/852: comprising tellurium, selenium or sulfur
- H10W 40/28: comprising Peltier coolers
- C01P 2006/40: Electric properties
- Y02P 20/129: Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- H10N: ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10W: GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

The p- or n-conductive semiconductor material comprises a compound of the general formula (I) SnaPb1-a-(x1+ . . . +xn)A1x1 . . . Anxn(Te1-p-q-rSepSqXr)1+z (I) where 0.05<a<1 n≧1 where n is the number of chemical elements different than Sn and Pb in each case independently 1 ppm≦x1 . . . xn≦0.05 A1 . . . An are different from one another and are selected from the group of the elements Li, Na, K, Rb, Cs, Mg, Ca, Y, Ti, Zr, Hf, Nb, Ta, Cr, Mn, Fe, Cu, Ag, Au, Ga, In, Tl, Ge, Sb, Bi X is F, Cl, Br or I 0≦p≦1 0≦q≦1 0≦r≦0.01 −0.01≦z≦0.01 with the condition that p+q+r≦1 and a+x1+ . . . +xn≦1.

## Claims

### Claim 1

A p- or n-conductive semiconductor material comprising a compound of formula (I)
SnaPb1-a-(x1+ . . . +xn)A1x1 . . . Anxn(Te1-p-q-rSepSqXr)1+z (I),
wherein
0.2≦a≦0.75;
n is ≧2, where n is a number of chemical elements different than Sn and Pb;
in each case independently
0.001≦x1, x2, . . . xn≦0.05;
A1, A2, . . . An are different from one another, A1 is selected from the group consisting of Ti, Zr, Hf, Mn, Ag, and Ge, and A2, . . . An are selected from the group consisting of Ti, Zr, and Hf;
X is F, Cl, Br, or I;
0≦p≦1;
0≦q≦1;
0≦r≦0.01; and
−0.01≦z≦0.01,
with the condition that a+x1+x2 . . . +xn<1 and the sum of x1 . . . xn is in the range of 0.002 to 0.1; and
wherein p-type condition does not switch to n-type condition with rising temperature.

### Claim 2 (depends on 1)

The semiconductor material according to claim 1, wherein n is 2.

### Claim 3 (depends on 2)

The semiconductor material according to claim 2 wherein A1 . . . An are Zr and Ge.

### Claim 4 (depends on 1)

The semiconductor material according to claim 1, wherein p=q=r=0.

### Claim 5 (depends on 1)

A process for producing a semiconductor material according to claim 1, the method comprising reactively grinding or co-melting mixtures of particular elemental constituents or alloys thereof.

### Claim 6 (depends on 5)

The process according to claim 5 comprising co-melting, wherein the co-melting is effected in an induction oven.

### Claim 7 (depends on 1)

A process for producing a semiconductor material according to claim 1, comprising:
(1) co-melting mixtures of the particular elemental constituents or alloys thereof with the at least quaternary or ternary compound, to obtain a first material;
(2) grinding the first material obtained in (1), to obtain a second material;
(3) pressing or extruding the second material obtained in (2) to moldings; and
(4) sintering the moldings obtained in (3).

### Claim 8 (depends on 2)

A process for producing a semiconductor material according to claim 2, comprising:
(1) co-melting mixtures of the particular elemental constituents or alloys thereof with the at least quaternary or ternary compound, to obtain a first material;
(2) grinding the first material obtained in (1), to obtain a second material;
(3) pressing or extruding the second material obtained in (2) to moldings; and
(4) sintering the moldings obtained in (3).

### Claim 9 (depends on 4)

A process for producing a semiconductor material according to claim 4, the method comprising reactively grinding or co-melting mixtures of particular elemental constituents or alloys thereof.

### Claim 10 (depends on 9)

The process according to claim 9 comprising co-melting, wherein the co-melting is effected in an induction oven.

### Claim 11 (depends on 4)

A process for producing a semiconductor material according to claim 4, comprising:
(1) co-melting mixtures of the particular elemental constituents or alloys thereof with the at least quaternary or ternary compound, to obtain a first material;
(2) grinding the first material obtained in (1), to obtain a second material;
(3) pressing or extruding the second material obtained in (2) to moldings; and
(4) sintering the moldings obtained in (3).

### Claim 12 (depends on 1)

A thermoelectric generator or Peltier arrangement comprising a semiconductor material according to claim 1.

### Claim 13 (depends on 12)

A heat pump, cooler, refrigerator, (laundry) drier, generator for utilizing heat sources, or generator for converting thermal energy to electrical energy, comprising at least one thermoelectric generator or one Peltier arrangement according to claim 12.

### Claim 14 (depends on 4)

A thermoelectric generator or Peltier arrangement comprising a semiconductor material according to claim 4.

### Claim 15 (depends on 14)

A heat pump, cooler, refrigerator, (laundry) drier, generator for utilizing heat sources, or generator for converting thermal energy to electrical energy, comprising at least one thermoelectric generator or one Peltier arrangement according to claim 14.