# US 2018/0323358 A1 · Method for pre-processing semiconducting thermoelectric materials for metallization, interconnection and bonding

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- Number: US 2018/0323358 A1
- Document ID: US20180323358A1
- Status: Published application
- Kind: A1
- Application number: 15/525,776
- Filed: 2015-11-11
- Published: 2018-11-08
- Earliest claimed: 2014-11-12
- Assignees: Tegma AS
- Applicants: Tegma AS
- Inventors: Torleif A. TOLLEFSEN; Marianne Aanvik ENGVOLL; Ole Martin LOVVIK; Andreas LARSSON
- Web page: https://patentgrep.com/patent/US20180323358A1

## CPC

- H10N 10/817: the junction being non-separable, e.g. being cemented, sintered or soldered
- B23K 35/262: {Sn as the principal constituent}
- H10N 10/01: Manufacture or treatment
- H10N 10/17: characterised by the structure or configuration of the cell or thermocouple forming the device
- H10N 10/853: comprising arsenic, antimony or bismuth (H10N10/852 takes precedence)
- B23K 2101/36: Electric or electronic devices
- H10N: ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- B23K: SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM

## Abstract

The present invention relates to a method for pre-processing semiconducting thermoelectric materials for metallization, interconnection and bonding to form a thermoelectric device, and thermoelectric devices utilising the pre-processed processing semiconducting thermoelectric materials made by the method, where a cost-effective, simple and resilient interconnection and bonding of semiconducting thermoelectric materials to the electrodes of thermoelectric devices is obtained by employing the solid-liquid interdiffusion bonding concept in combination with use of an adhesion layer/diffusion barrier layer/adhesion layer structure (interchangeably also termed as; the ADA-structure) in-between the solid-liquid interdiffusion bonding layers and the semiconducting thermoelectric material.

## Claims

### Claim 1

A method for forming a pre-processed semiconducting thermoelectric conversion material for metallization, interconnection and bonding, wherein the method comprises the following process steps in successive order:
employing at least one element of a n-type or p-type doped semiconducting thermoelectric conversion material having a first and second surface on opposite sides,
placing the at least one element of semiconducting thermoelectric conversion material into a deposition chamber, and then:
i) depositing a first adhesion layer of a first metal directly onto the first and the second surface of the element of the semiconducting thermoelectric conversion material,
ii) depositing a diffusion barrier layer of a non-metallic compound of a second metal directly onto the first adhesion layer on the first and second surface of the semiconducting thermoelectric conversion material element,
iii) depositing a second adhesion layer of a third metal directly onto the diffusion barrier layer of the non-metallic compound of the second metal on the first and second surface of the element of the semiconducting thermoelectric conversion material,
wherein
the deposition chamber is either a chemical vapour deposition chamber, a physical vapour deposition chamber, or an atomic deposition chamber, and the deposition of the different layers of steps i) to iii) is obtained by feeding pre-cursor gases with varying chemical composition into the deposition chamber,
the non-metallic compound of the second metal is either a nitride or an oxide of the second metal,
depositing a first bonding layer of a metal A directly onto the second adhesion layer on the first and second surface of element of the semiconducting thermoelectric conversion material, and
depositing a second bonding layer of a metal B directly onto the first bonding layer the on the first and second surface of the element of the semiconducting thermoelectric conversion material,
wherein
the melting point of metal A is higher than metal B and metal B is chemically reactive towards metal A at their common interface when subject to heating above the melting point of metal B forming an intermetallic compound by solid-liquid interdiffusion.

### Claim 2 (depends on 1)

A method according to claim 1, wherein the semiconducting thermoelectric conversion material is a filled or non-filled CoSb3-based skutterudite.

### Claim 3 (depends on 1)

A method according to claim 1, wherein the first metal of the first adhesion layer and the second metal of the second adhesion layer is of the same elementary metal, and where the non-metallic compound of the second metal of the diffusion barrier layer is a nitride or an oxide of the same elementary metal as the first and second metal.

### Claim 4 (depends on 3)

A method according to claim 3, wherein the elementary metal of the first metal of the first adhesion layer and the second metal of the second adhesion layer is one of Cr, Cu, Sn, Ta, and Ti, and the non-metallic compound of the second metal of the diffusion barrier layer is a nitride or an oxide of one of Cr, Cu, Sn, Ta, and Ti.

### Claim 5 (depends on 1)

A method according to claim 1, wherein the metal A of the first bonding layer is one of the following elementary metals; Au, Ag, Cu, Ni, Ni—V alloy with from 6.5 to 7.5 atom % V, and the metal B of the second bonding layer is one of the following elementary metals; In or Sn.

### Claim 6 (depends on 1)

A method according to claim 1, wherein the first and second metal is Ti of at least 99.5 weight % purity, the non-metallic compound of the second metal of the diffusion barrier layer is TiN, the metal A of the first bonding layer is Ni and the metal B of the second bonding layer is Sn.

### Claim 7 (depends on 1)

A method according to claim 1, wherein:
the thickness of the first adhesion layer is in one of the following ranges; from 20 nm to 2 μm, from 50 nm to 1.5 μm, from 100 nm to 1.5 μm, from 200 nm to 1.5 μm, or from 500 nm to 1.5 μm,
the thickness of the diffusion barrier layer is in one of the following ranges: from, 50 to 5000 nm, from 75 to 3000 nm, from 100 to 2000 nm, from 150 to 1000 nm, from 150 to 750 nm, from 200 to 500 nm, from 200 to 400 nm or from 200 to 300 nm,
the thickness of the second adhesion layer is in one of the following ranges; from 20 nm to 1000 nm, from 30 nm to 750 nm, from 40 nm to 500 nm, from 100 nm to 400 nm, or from 150 nm to 300 nm,
the thickness of the first bonding layer of metal A is in one of the following ranges; from 1 μm to 1 cm, from 1 μm to 0.5 cm, from 1 μm to 0.1 cm, from 2 μm to 500 μm, from 2 μm to 100 μm, from 2 μm to 50 μm, or from 3 μm to 10 μm, and
the thickness of the second bonding layer of metal B is in one of the following ranges; from 300 nm to 0.75 cm, 300 nm to 0.3 cm, 300 nm to 750 μm, from 200 nm to 400 μm, from 200 nm to 75 μm, from 200 nm to 30 μm, or from 300 nm to 3 μm.

### Claim 8 (depends on 1)

A method according to claim 1, wherein the method further comprises depositing a 10 to 50 nm thick layer of Au directly onto one of the first adhesion layer, the second adhesion layer, or the first bonding layer, or two or more of these.

### Claim 9 (depends on 1)

A method according to claim 1, wherein the first and second bonding layers of metal A and B, respectively, is deposited by:
depositing by vapour deposition the first bonding layer of a metal A directly onto the second adhesion layer on the first and second surface of element of the semiconducting thermoelectric conversion material and the second bonding layer of a metal B directly onto the first bonding layer the on the first and second surface of the element of the semi-conducting thermoelectric conversion material in the same vapour deposition chamber applied for deposition of the first adhesion layer, the diffusion barrier layer and the second adhesion layer structure, or by:
depositing the first and second bonding layers by electroplating or by electro-less plating.

### Claim 10

A thermoelectric device, comprising:
a number of N thermoelectric elements of semiconducting thermoelectric conversion material doped to n-type conductivity and a number of N thermoelectric elements of semiconducting thermoelectric conversion material doped to p-type conductivity, where N is an integer from 1 to n,
a number of 2N+1 electric contact elements comprising a first bonding layer of a metal A and a second bonding layer of a metal B, and
a first substrate in thermal contact with a heat reservoir and second substrate in thermal contact with a heat sink,
where
the N thermoelectric elements of n-type conductivity and the N thermoelectric elements of p-type conductivity are electrically connected in series by the 2N+1 electric contact elements,
the thermoelectric elements are bonded to the electric contact elements by solid liquid interdiffusion bonds, and
the thermoelectric elements are on a first side in thermal contact with the first substrate in thermal contact with a heat reservoir, and on a second side opposite the first side, the thermoelectric elements are on a second side opposite the first side in thermal contact with the second substrate in thermal contact with a heat sink, characterised in that
each of the N thermoelectric elements of n-type conductivity and the N thermoelectric elements of p-type conductivity have on their first and second surface:
i) a first adhesion layer of a first metal deposited directly onto the first and second surfaces,
ii) a diffusion barrier layer of a non-metallic compound of a second metal deposited directly onto the first adhesion layer on the first and second surfaces,
iii) a second adhesion layer of a third metal deposited directly onto the diffusion barrier layer of the non-metallic compound of the second metal on the first and second surfaces,
iv) a first bonding layer of a metal A deposited directly onto the second adhesion layer on the first and second surfaces, and
v) a second bonding layer of a metal B deposited directly onto the first bonding layer the on the first and second surfaces,
where
the non-metallic compound of the second metal is either a nitride or an oxide of the second metal,
the melting point of metal A is higher than metal B and metal B is chemically reactive towards metal A at their common interface when subject to heating above the melting point of metal B, and
the solid liquid interdiffusion bonds are formed by laying the second bonding layer of metal B of the thermoelectric elements and the electric contact elements, respectively, facing and contacting each other followed by an annealing which causes metal B of the second bonding layer to melt and reacting with metal A of the first bonding layer.

### Claim 11 (depends on 10)

A thermoelectric device according to claim 10, wherein the semiconducting thermoelectric conversion material is a filled or non-filled CoSb3-based skutterudite.

### Claim 12 (depends on 10)

A thermoelectric device according to claim 10, wherein the first metal of the first adhesion layer and the second metal of the second adhesion layer is of the same elementary metal, and where the non-metallic compound of the second metal of the diffusion barrier layer is a nitride or an oxide of the same elementary metal as the first and second metal.

### Claim 13 (depends on 12)

A thermoelectric device according to claim 12, wherein the elementary metal of the first metal of the first adhesion layer and the second metal of the second adhesion layer is one of Cr, Cu, Sn, Ta, and Ti, and the non-metallic compound of the second metal of the diffusion barrier layer is a nitride or an oxide of one of Cr, Cu, Sn, Ta, and Ti.

### Claim 14 (depends on 10)

A thermoelectric device according to claim 10, wherein the metal A of the first bonding layer is one of the following elementary metals; Au, Ag, Cu, Ni, Ni—V alloy with from 6.5 to 7.5 atom % V, and the metal B of the second bonding layer is one of the following elementary metals; In or Sn.

### Claim 15 (depends on 10)

A thermoelectric device according to claim 10, wherein the first and second metal is Ti of at least 99.5 weight % purity, the non-metallic compound of the second metal of the diffusion barrier layer is TiN, the metal A of the first bonding layer is Ni and the metal B of the second bonding layer is Sn.

### Claim 16 (depends on 10)

A thermoelectric device according to claim 10, wherein:
the thickness of the first adhesion layer is in one of the following ranges; from 20 nm to 2 μm, from 50 nm to 1.5 μm, from 100 nm to 1.5 μm, from 200 nm to 1.5 μm, or from 500 nm to 1.5 μm,
the thickness of the diffusion barrier layer is in one of the following ranges: from, 50 to 5000 nm, from 75 to 3000 nm, from 100 to 2000 nm, from 150 to 1000 nm, from 150 to 750 nm, from 200 to 500 nm, from 200 to 400 nm or from 200 to 300 nm,
the thickness of the second adhesion layer is in one of the following ranges; from 20 nm to 1000 nm, from 30 nm to 750 nm, from 40 nm to 500 nm, from 100 nm to 400 nm, or from 150 nm to 300 nm,
the thickness of the first bonding layer of metal A is in one of the following ranges; from 1 μm to 1 cm, from 1 μm to 0.5 cm, from 1 μm to 0.1 cm, from 2 μm to 500 μm, from 2 μm to 100 μm, from 2 μm to 50 μm, or from 3 μm to 10 μm, and
the thickness of the second bonding layer of metal B is in one of the following ranges; from 300 nm to 0.75 cm, 300 nm to 0.3 cm, 300 nm to 750 μm, from 200 nm to 400 μm, from 200 nm to 75 μm, from 200 nm to 30 μm, or from 300 nm to 3 μm.

### Claim 17 (depends on 10)

A thermoelectric device according to claim 10, wherein the method further comprises depositing a 10 to 50 nm thick layer of Au directly onto one of the first adhesion layer, the second adhesion layer, or the first bonding layer, or two or more of these.