# US 9,040,339 B2 · Practical method of producing an aerogel composite continuous thin film thermoelectric semiconductor material

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- Number: US 9,040,339 B2
- Document ID: US9040339B2
- Status: Granted
- Kind: B2
- Application number: 14/042,729
- Filed: 2013-10-01
- Published: 2015-04-02
- Granted: 2015-05-26
- Earliest claimed: 2013-10-01
- Applicants: The Pen
- Inventors: The Pen
- Web page: https://patentgrep.com/patent/US9040339B2

## CPC

- H10N 10/01: Manufacture or treatment
- B01J 13/0091: {Preparation of aerogels, e.g. xerogels}
- H10N: ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS

## Abstract

A method is disclosed of constructing a composite material structure, comprised of an aerogel precursor foundation, which is then overlaid throughout its interior with an even and continuous thin layer film of doped thermoelectric semiconductor such that electrical current is transmitted as a quantum surface phenomena, while the cross-section for thermal conductivity is kept low, with the aerogel itself dissipating that thermal conductivity. In one preferred embodiment this is achieved using a modified successive ionic layer adsorption and reaction in the liquid phase.

## Claims

### Claim 1

A method of producing an aerogel composite continuous thin film layer thermoelectric semiconductor material comprising
a) A wet phase formulation of an aerogel precursor gel,
b) Equilibrating the said aerogel precursor gel in a solution of metallic cations such that they coordinate evenly as a layer with the surface of the said aerogel precursor gel throughout its interior,
c) Equilibrating the said aerogel precursor gel in a solution of anions or anion equivalents that will deposit as an insoluble material upon reaction with the said metallic cations coordinated with the surface of the said aerogel precursor gel, whereupon additional anions or anion equivalents coordinate evenly as a layer with the surface of the said aerogel precursor gel throughout its interior,
d) Repetition of steps 1(b) and 1(c), where
(i) in step 1(b) the said metallic cations additionally react with any of the said anions or anion equivalents already coordinated with the surface of the said aerogel precursor gel throughout its interior and deposit as the said insoluble material,
(ii) until a thin film layer of the said insoluble material of the desired even thickness is obtained throughout the interior of said aerogel precursor gel,
e) Drying the said aerogel precursor gel to remove the liquid phase.

### Claim 2 (depends on 1)

The method of claim 1 where the said drying is performed by supercritical drying.

### Claim 3 (depends on 1)

The method of claim 1 where the said aerogel precursor gel is sufficiently strengthened and hydrophobic from the deposit of the said insoluble material that it can be dried under ambient conditions, or optionally with the application of moderate heat and/or vacuum.

### Claim 4 (depends on 1)

The method of claim 1 where the thickness of the said aerogel precursor gel is 1 mm or greater.

### Claim 5 (depends on 1)

The method of claim 1 where the said metallic cations are selected from the group of the transitional metals on the periodic table in groups 3-11 together with the poor metals on the periodic table in groups 12-15.

### Claim 6 (depends on 1)

The method of claim 1 where the concentration of the said cations and the concentration of said anions or anion equivalents are optimally in the range of 0.05 to 0.20 molar.

### Claim 7 (depends on 1)

The method of claim 1 where the optimum said even thickness is in the range of 0.2 nm to 10 nm.

### Claim 8 (depends on 5)

The method of claim 5 where the said metallic cations comprise at least two different cations.

### Claim 9 (depends on 5)

The method of claim 5 where in step 1(d) the repetition of step 1(b) is done with a solution of the said metallic cations of a different composition.

### Claim 10 (depends on 1)

The method of claim 1 where complexing anions are added to the said solution of metallic cations to stabilize them.

### Claim 11 (depends on 1)

The method of claim 1 where the said anions or anion equivalents are comprised of at least one selected from the group which will form a sulfide, selenide, telluride, arsenide, antimonide or an oxide.

### Claim 12 (depends on 11)

The method of claim 11 where in step 1(d) the repetition of step 1(c) is done with a solution of the said anions or anion equivalents of different composition.

### Claim 13 (depends on 1)

The method of claim 1 where after either of the steps 1(b) and 1(c) is performed, the said aerogel precursor gel is back equilibrated in pure solvent.

### Claim 14 (depends on 1)

The method of claim 1 where the said aerogel precursor gel is comprised of silica.

### Claim 15 (depends on 1)

The method of claim 1 where the said aerogel precursor gel contains the oxide of at least one metallic atom selected from the group of the transitional metals on the periodic table in groups 3-11 together with the poor metals on the periodic table in groups 12-15.

### Claim 16 (depends on 1)

The method of claim 1 where after the said drying the said thin film layer is annealed using inductive or microwave heating.

### Claim 17 (depends on 16)

The method of claim 16, done under an inert atmosphere.

### Claim 18 (depends on 16)

The method of claim 16, done under an atmosphere that includes a gas component acting as a dopant of the said semiconductor material.

### Claim 19 (depends on 1)

The method of claim 1 where at least one of the said solution of metallic cations or the said solution of anions or anion equivalents is raised to a temperature in the range of 50-90 C to increase diffusion rates.

### Claim 20 (depends on 1)

An aerogel composite continuous thin film layer thermoelectric semiconductor material produced in accordance with the method of claim 1.
