# US 9,520,563 B2 · Patterning of organic semiconductor materials

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- Number: US 9,520,563 B2
- Document ID: US9520563B2
- Status: Granted
- Kind: B2
- Application number: 12/743,772
- Filed: 2008-11-20
- Published: 2010-12-09
- Granted: 2016-12-13
- Earliest claimed: 2007-11-21
- Assignees: The Board of Trustees of the Leland Stanford Junior University
- Applicants: Stefan Christian Bernhardt Mannsfeld; Armon Sharei; Zhenan Bao
- Inventors: Stefan Christian Bernhardt Mannsfeld; Armon Sharei; Zhenan Bao
- Web page: https://patentgrep.com/patent/US9520563B2

## CPC

- H10K 71/12: using liquid deposition, e.g. spin coating
- H10K 71/191: {characterised by provisions for the orientation or alignment of the layer to be deposited}
- H10K 10/464: {Lateral top-gate IGFETs comprising only a single gate}
- H10K 85/113: {Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene}
- H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES

## Abstract

Organic semiconductor material can be patterned from a solution onto a substrate by selectively wetting the substrate with the solution while applying a mechanical disturbance (such as stirring the solution while the substrate is immersed, or wiping the solution on the substrate). The organic semiconductor material can then be precipitated out of the solution, for example to bridge gaps between source and drain electrodes to form transistor devices. In some embodiments, the solution containing the organic semiconductor material can be mixed in an immiscible host liquid. This can allow the use of higher concentration solutions while also using less of the organic semiconductor material.

## Claims

### Claim 1

A method for manufacturing organic semiconductor devices on a substrate having an array of electrode pairs, the method comprising:
selectively wetting the electrode pairs with a solution of organic semiconductor material while a mechanical disturbance is applied to the solution; and
precipitating the organic semiconductor material from the solution to bridge gaps between the electrodes in the electrode pairs, wherein the mechanical disturbance comprises stirring the solution while the substrate is immersed in a mixture containing the solution in an immiscible host liquid.

### Claim 2 (depends on 1)

The method of claim 1, wherein the mechanical disturbance comprises wiping the solution onto the substrate.

### Claim 3 (depends on 1)

The method of claim 1, further comprising modifying a surface of the substrate to promote selective wetting of the electrode pairs by the solution.

### Claim 4

A method for manufacturing organic semiconductor devices on a substrate having an array of electrode pairs, the method comprising:
selectively wetting the electrode pairs with a solution of organic semiconductor material using a mixture of the solution residing in an immiscible host liquid; and
precipitating the organic semiconductor material from the solution to bridge gaps between the electrodes in the electrode pairs.

### Claim 5 (depends on 4)

The method of claim 4, further comprising modifying a surface of the substrate to promote selective wetting of the electrode pairs by the solution.

### Claim 6 (depends on 4)

The method of claim 4, further comprising immersing the substrate in the mixture.

### Claim 7 (depends on 6)

The method of claim 6, further comprising stirring the mixture while the substrate is immersed.

### Claim 8 (depends on 7)

The method of claim 7, wherein stirring the mixture creates a vortex in the mixture.

### Claim 9 (depends on 6)

The method of claim 6, further comprising heating the mixture while the substrate is immersed.

### Claim 10 (depends on 4)

The method of claim 4, wherein precipitation of the organic semiconductor material is performed under conditions that promote single crystal growth.

### Claim 11 (depends on 4)

The method of claim 4, further comprising connecting source and drain leads to respective electrodes in the pairs of electrodes.

### Claim 12 (depends on 4)

The method of claim 4, wherein the organic semiconductor material is an oligothiophene.

### Claim 13 (depends on 4)

The method of claim 4, wherein the solution is a saturated or nearly saturated solution.

### Claim 14 (depends on 4)

The method of claim 4, wherein the host liquid has a high boiling point of at least 180° C.

### Claim 15 (depends on 4)

The method of claim 4, wherein the host liquid is a halogenated solvent.

### Claim 16 (depends on 4)

The method of claim 4, wherein the substrate comprises silicon.

### Claim 17 (depends on 4)

The method of claim 4, wherein the substrate is flexible.

### Claim 18 (depends on 4)

The method of claim 4, further comprising modifying the electrode pairs to increase lyophilicity.

### Claim 19 (depends on 4)

The method of claim 4, wherein the gaps between electrode pairs are about 10 microns or less.

### Claim 20 (depends on 4)

The method of claim 4, wherein the mixture has a liquid host to solution volume ratio of 500:1 or greater.

### Claim 21

A method of patterning a material on selected areas on a substrate surface, the method comprising:
forming a solution of the material in a solvent;
forming an immiscible mixture of the solution in a host liquid; and
exposing the substrate surface to the mixture so that the solution selectively wets the selected areas.

### Claim 22 (depends on 21)

The method of claim 21, wherein the solvent is more dense than the host liquid.

### Claim 23 (depends on 21)

The method of claim 21, wherein the selected areas of the substrate comprise lyophilic regions surrounded by a lyophobic background.

### Claim 24 (depends on 1)

A semiconductor device made using the method as recited in claim 1.

### Claim 25 (depends on 24)

A semiconductor transistor device having attributes ensuing from a method as recited in claim 24.

### Claim 26 (depends on 21)

A semiconductor device made using the method as recited in claim 21.

### Claim 27 (depends on 1)

The method of claim 1, wherein selectively wetting the electrode pairs with a solution of organic semiconductor material includes introducing an organic semiconductor material to a surface of the substrate having lyophobic regions that are adjacent other regions including the electrode pairs, and using the lyophobic regions to mitigate the wetting of the substrate at the lyophobic regions, while wetting regions of the surface that include the electrode pairs.

### Claim 28

A method for manufacturing organic semiconductor devices on a substrate having an array of electrode pairs, the method comprising:
selectively wetting the electrode pairs with a solution of organic semiconductor material while a mechanical disturbance is applied to the solution, wherein selectively wetting the electrode pairs with a solution of organic semiconductor material includes introducing an organic semiconductor material to a surface of the substrate having lyophobic regions that are adjacent other regions including the electrode pairs, and using the lyophobic regions to mitigate the wetting of the substrate at the lyophobic regions, while wetting regions of the surface that include the electrode pairs; and
precipitating the organic semiconductor material from the solution to bridge gaps between the electrodes in the electrode pairs; and applying the mechanical disturbance by applying a disturbance to generate shearing forces that are sufficient to mitigate wetting of the lyophobic regions and that are insufficient to mitigate wetting of the electrode pairs.

### Claim 29

A method for manufacturing organic semiconductor devices on a substrate having an array of electrode pairs, the method comprising:
selectively wetting the electrode pairs with a solution of organic semiconductor material while a mechanical disturbance is applied to the solution, wherein selectively wetting the electrode pairs with a solution of organic semiconductor material includes introducing an organic semiconductor material to a surface of the substrate having lyophobic regions that are adjacent other regions including the electrode pairs, and using the lyophobic regions to mitigate the wetting of the substrate at the lyophobic regions, while wetting regions of the surface that include the electrode pairs; and
precipitating the organic semiconductor material from the solution to bridge gaps between the electrodes in the electrode pairs; and applying a disturbance to generate shearing forces that are sufficient to mitigate wetting of the lyophobic regions and sufficient to mitigate the formation of droplets covering at least two electrode pairs, and that are insufficient to mitigate wetting of individual electrode pairs.

### Claim 30 (depends on 4)

The method of claim 4, wherein selectively wetting the electrode pairs with a solution of organic semiconductor material includes introducing the organic semiconductor material to a surface of the substrate having lyophobic regions that are adjacent other regions including the electrode pairs, and using the lyophobic regions to mitigate the wetting of the substrate at the lyophobic regions, and forming droplets of the solution at regions of the surface that include the electrode pairs.

### Claim 31 (depends on 21)

The method of claim 21, wherein exposing the substrate surface to the mixture so that the solution selectively wets the selected areas includes selectively wetting the selected areas while using lyophobic characteristics of other areas of the substrate surface to mitigate wetting of the other areas.

### Claim 32 (depends on 1)

The method of claim 1, wherein selectively wetting the electrode pairs includes selectively wetting electrode pairs on a planar surface of the substrate, each respective pair of electrodes being laterally adjacent another pair of electrodes and laterally separated from the other pair of electrodes by an exposed planar region of the substrate surface, by using hydrophobic characteristics of the planer region to form droplets of the solution bridging the gap between the electrodes in each pair and to mitigate the formation of droplets in the exposed planar region between the electrode pairs.

### Claim 33 (depends on 4)

The method of claim 4, wherein selectively wetting the electrode pairs includes selectively wetting electrode pairs on a planar surface of the substrate, each respective pair of electrodes being laterally adjacent another pair of electrodes and laterally separated from the other pair of electrodes by an exposed planar region of the substrate surface, by using hydrophobic characteristics of the planer region to form droplets of the solution bridging the gap between the electrodes in each pair and to mitigate the formation of droplets in the exposed planar region between the electrode pairs.

### Claim 34 (depends on 21)

The method of claim 21, wherein exposing the substrate surface to the mixture so that the solution selectively wets the selected areas includes selectively wetting selected areas on the surface of the substrate, each selected area being laterally separated from another one of the selected areas by an exposed planar region of the substrate surface, by using hydrophobic characteristics of the planer regions between each selected area to form droplets of the solution in the selected areas and to mitigate the formation of droplets in the exposed planar region between the selected areas.