# US 2013/0157435 A1 · Materials and Methods of Forming Controlled Void

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- Number: US 2013/0157435 A1
- Document ID: US20130157435A1
- Status: Published application
- Kind: A1
- Application number: 13/767,409
- Filed: 2013-02-14
- Published: 2013-06-20
- Earliest claimed: 2006-04-18
- Assignees: Air Products and Chemicals, Inc.
- Inventors: Raymond Nicholas Vrtis; Dingjun Wu; Mark Leonard O'Neill; Mark Daniel Bitner; Jean Louise Vincent; Eugene Joseph Karwacki, JR.; Aaron Scott Lukas
- Web page: https://patentgrep.com/patent/US20130157435A1

## CPC

- H10P 14/6902: {composed of carbon, e.g. alpha-C, diamond or hydrogen doped carbon}
- H10P 14/6328: {Deposition from the gas or vapour phase}
- H10P 14/6342: {Liquid deposition, e.g. spin-coating, sol-gel techniques or spray coating}
- H10P 14/668: {the materials being characterised by the deposition precursor materials}
- H10P 14/6938: {the material containing at least one metal element, e.g. metal oxides, metal oxynitrides or metal oxycarbides}
- H10P 34/40: with high-energy radiation
- H10P 50/642: {Chemical etching}
- H10W 10/021: {of air gaps}
- H10W 10/20: Air gaps
- H10W 20/072: {of dielectric parts comprising air gaps}
- H10W 20/46: comprising air gaps
- H10P 14/6336: {in the presence of a plasma [PECVD]}
- H10P 14/665: {Porous materials}
- H10P 14/6686: {the compound being a molecule comprising at least one silicon-oxygen bond and the compound having hydrogen or an organic group attached to the silicon or oxygen, e.g. a siloxane}
- H10P 14/6922: {the material containing Si, O and at least one of H, N, C, F or other non-metal elements, e.g. SiOC, SiOC:H or SiONC}
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
- H10W: GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10

## Abstract

The present invention is a process for forming an air gap within a substrate, the process comprising: providing a substrate; depositing a sacrificial material by deposition of at least one sacrificial material precursor; depositing a composite layer; removal of the porogen material in the composite layer to form a porous layer and contacting the layered substrate with a removal media to substantially remove the sacrificial material and provide the air gaps within the substrate; wherein the at least one sacrificial material precursor is selected from the group consisting of: an organic porogen; silicon, and a polar solvent soluble metal oxide and mixtures thereof.

## Claims

### Claim 1

A process for forming an air gap, the process comprising:
(a) providing a substrate;
(b) depositing a sacrificial layer with at least one organic precursor onto the substrate;
(c) depositing a composite layer with a porogen that is the at least one organic precursor in (b) and at least one silica-containing precursor or organosilicate glass(OSG) precursor onto the substrate;
(d) applying energy to the substrate having the sacrificial layer and the composite layer to remove both the sacrificial layer to provide air gaps and the porogen to form a porous layer; and
Wherein
the at least one organic precursor is at least one member selected from the group consisting of:
(1) at least one cyclic hydrocarbon having a cyclic structure and the formula CnH2n, where n is 4 to 14, a number of carbons in the cyclic structure is between 4 and 10, and the at least one cyclic hydrocarbon optionally contains a plurality of simple or branched hydrocarbons substituted onto the cyclic structure;
(2) at least one linear or branched, saturated, singly or multiply unsaturated hydrocarbon of the general formula CnH(2n+2)−2y where n is 2 to 20 and where y is 0 to n;
(3) at least one singly or multiply unsaturated cyclic hydrocarbon having a cyclic structure and the formula CnH2n−2x, where x is a number of unsaturated sites, n is 4 to 14, a number of carbons in the cyclic structure is between 4 and 10, and the at least one singly or multiply unsaturated cyclic hydrocarbon optionally contains a plurality of simple or branched hydrocarbons substituents substituted onto the cyclic structure, and contains endocyclic unsaturation or unsaturation on one of the hydrocarbon substituents;
(4) at least one bicyclic hydrocarbon having a bicyclic structure and the formula CnH2n−2, where n is 4 to 14, a number of carbons in the bicyclic structure is from 4 to 12, and the at least one bicyclic hydrocarbon optionally contains a plurality of simple or branched hydrocarbons substituted onto the bicyclic structure;
(5) at least one multiply unsaturated bicyclic hydrocarbon having a bicyclic structure and the formula CnH2n−(2+2x), where x is a number of unsaturated sites, n is 4 to 14, a number of carbons in the bicyclic structure is from 4 to 12, and the at least one multiply unsaturated bicyclic hydrocarbon optionally contains a plurality of simple or branched hydrocarbons substituents substituted onto the bicyclic structure, and contains endocyclic unsaturation or unsaturation on one of the hydrocarbon substituents;
(6) at least one tricyclic hydrocarbon having a tricyclic structure and the formula CnH2n−4, where n is 4 to 14, a number of carbons in the tricyclic structure is from 4 to 12, and the at least one tricyclic hydrocarbon optionally contains a plurality of simple or branched hydrocarbons substituted onto the cyclic structure;
(7) at least one hydrocarbon structures containing one or more alcohol groups and having the general formula CnH2n+2−2x−2y−z(OH)z where n is 1 to 12, and where x is the number of cyclic rings in the structure and is between 0 and 4, and where y is the number of unsaturated bonds in the structure and is between 0 and n, and where z is the number of alcohol groups in the compounds and is between 1 and 4, and where the alcohol functionality can be exo- and/or endocyclic;
(8) at least one hydrocarbon structures containing one or more ether groups and having the general formula CnH2n+2−2x−2yOz where n is 1 to 12, and where x is the number of cyclic rings in the structure and is between 0 and 4, and where y is the number of unsaturated bonds in the structure and is between 0 and n, and where z is the number of ether linkages in the structure and is between 1 and 4, and where the ether linkage(s) can be exo- and/or endocyclic;
(9) at least one hydrocarbon structures containing one or more epoxide groups and having the general formula CnH2n+2−2x−2y−2zOz where n is 1 to 12, and where x is the number of cyclic rings in the structure and is between 0 and 4, and where y is the number of unsaturated bonds in the structure and is between 0 and n, and where z is the number of epoxide groups in the structure and is between 1 and 4, and where the epoxide groups can be attached to a cyclic ring or a linear chain;
(10) at least one hydrocarbon structures containing one or more aldehyde groups and having the general formula CnH2n+2−2x−2y−2zOz where n is 1 to 12, and where x is the number of cyclic rings in the structure and is between 0 and 4, and where y is the number of unsaturated bonds in the structure and is between 0 and n, and where z is the number of aldehyde groups in the structure and is between 1 and 4;
(11) at least one hydrocarbon structures containing one or more ketone groups and having the general formula CnH2n+2−2x−2y−2zOz where n is 1 to 12, and where x is the number of cyclic rings in the structure and is between 0 and 4, and where y is the number of unsaturated bonds in the structure and is between 0 and n, and where z is the number of aldehyde groups in the structure and is between 1 and 4, and where the ketone group(s) can be exo- and/or endocyclic;
(12) at least one hydrocarbon structures containing one or more carboxylic acid groups and having the general formula CnH2n+2−2x−2y−3z(OOH)z where n is 1 to 12, and where x is the number of cyclic rings in the structure and is between 0 and 4, and where y is the number of unsaturated bonds in the structure and is between 0 and n, and where z is the number of carboxylic acid groups in the structure and is between 1 and 4;
(13) at least one hydrocarbon structures containing an even number of carboxylic acid groups and in which the acid functionality is dehydrated to form a cyclic anhydride group where the structures have the general formula CnH2n+2−2x−2y−6z(O3)z where n is 1 to 12, and where x is the number of cyclic rings in the structure and is between 0 and 4, and where y is the number of unsaturated bonds in the structure and is between 0 and n, and where z is the number of anhydride groups in the structure and is 1 or 2;
(14) at least one hydrocarbon structures containing an ester group with the general formula CnH2n+2−2x−2y−2z(O2)z where n is 1 to 12, and where x is the number of cyclic rings in the structure and is between 0 and 4, and where y is the number of unsaturated bonds in the structure, and where none of the unsaturated bonds are conjugated with the carbonyl group of the ester, and where z is the number of anhydride groups in the structure and is 1 or 2;
(15) at least one hydrocarbon structures containing an acrylate functionality consisting of an ester group and at least one unsaturated bond that is conjugated with the carbonyl of the ester group, and having the general formula CnH2n+2−2x−2y−2z(O2)z where n is 1 to 12 and where x is the number of cyclic rings in the structure and is between 0 and 4, and where y is the number of unsaturated bonds in the structure and is greater than or equal to 1, and where at least of the unsaturated bonds are conjugated with the carbonyl group of the ester, and where z is the number of ester groups in the structure and is 1 or 2;
(16) at least one hydrocarbon structures containing both ether and a carbonyl functional groups and having the general formula CnH2n+2−2w−2x−2y(O)y(O)z where n is 1 to 12, and where w is the number of cyclic rings in the structure and is between 0 and 4, and where x is the number of unsaturated bonds in the structure and is between 0 and n, and where y is the number of carbonyl groups in the structure in which the carbonyl group can be ketones and/or aldehydes, and where z is the number of ether groups in the structure and is 1 or 2, and where the ether group(s) can be endocyclic or exocyclic;
(17) at least one hydrocarbon structures containing both ether and alcohol functional groups and having the general formula CnH2n+2−2w−2x−y(OH)y(O)z where n is 1 to 12, and where w is the number of cyclic rings in the structure and is between 0 and 4, and where x is the number of unsaturated bonds in the structure and is between 0 and n, and where y is the number of alcohol groups in the structure, and where z is the number of ether groups in the structure and is 1 or 2, and where the ether qroup(s) can be endocyclic or exocyclic;
(18) at least one hydrocarbon structures containing any combination of functional groups selected from the following list: alcohol, ether, carbonyl, and carboxylic acid and having the general formula CnH2n+2−2u−2y−w−2y−3z(OH)w(O)x(O)y(OOH)z where n is 1 to 12, and where u is the number of cyclic rings in the structure and is between 0 and 4, and where v is the number of unsaturated bonds in the structure and is between 0 and n, and where w is the number of alcohol groups in the structure and is between 0 and 4, and where x is the number of ether groups in the structure and is between 0 and 4 and where the ether group(s) can be endocyclic or exocyclic, and where y is the number of carbonyl groups in the structure and is between 0 and 3 in which the carbonyl group can be ketones and/or aldehydes, and where z is the number of carboxylic acid groups in the structure and is between 0 and 2;
(19) at least one hydrocarbon structures containing one or more primary amine groups and having the general formula CnH2n+2−2x−2y−z(NH2)z where n is 1 to 12, and where x is the number of cyclic rings in the structure and is between 0 and 4, and where y is the number of unsaturated bonds in the structure and is between 0 and n, and where z is the number of amine groups in the compounds and is between 1 and 4, and where the amine functionality can be exo- and/or endocyclic;
(20) at least one hydrocarbon structures containing one or more secondary amine groups and having the general formula CnH2n+2−2x−2y−2z(NH)z where n is 1 to 12, and where x is the number of cyclic rings in the structure and is between 0 and 4, and where y is the number of unsaturated bonds in the structure and is between 0 and n, and where z is the number of secondary amine groups in the compounds and is between 1 and 4, and where the amine functionality can be exo- and/or endocyclic;
(21) at least one hydrocarbon structures containing one or more tertiary amine groups and having the general formula CnH2n+2−2x−2y−3z(N)z where n is 1 to 12, and where x is the number of cyclic rings in the structure and is between 0 and 4, and where y is the number of unsaturated bonds in the structure and is between 0 and n, and where z is the number of tertiary amine groups in the compounds and is between 1 and 4, and where the amine functionality can be exo- and/or endocyclic;
(22) at least one hydrocarbon structures containing one or more nitro groups and having the general formula CnH2n+2−2x−2y−z(NO2)z where n is 1 to 12, and where x is the number of cyclic rings in the structure and is between 0 and 4, and where y is the number of unsaturated bonds in the structure and is between 0 and n, and where z is the number of nitro groups in the compounds and is between 1 and 4, and where the nitro functionality can be exo- and/or endocyclic;
(23) at least one hydrocarbon structures having both amine and ether functional groups having the general formula CnH2n+2−2u−2y−w−2x−3y−z(NH2)w(NH)x(N)y(OH)z where n is 1 to 12, and where u is the number of cyclic rings in the structure and is between 0 and 4, and where v is the number of unsaturated bonds in the structure and is between 0 and n, and where w is the number of primary amine groups, x is the number of secondary amine groups, y is the number of tertiary amine groups, and where 1<w+x+y<4, and where z is the number of alcohol groups in the compound and is between 1 and 4, and where the alcohol and/or amine groups can be exo- and/or endocyclic;
(24) at least one hydrocarbon structures having both amine and alcohol functional groups having the general formula CnH2n+2−2u−2y−w−2x−3y−z(NH2)w(NH)x(N)y(OH)z where n is 1 to 12, and where u is the number of cyclic rings in the structure and is between 0 and 4, and where v is the number of unsaturated bonds in the structure and is between 0 and n, and where w is the number of primary amine groups, x is the number of secondary amine groups, y is the number of tertiary amine groups, and where 1<w+x+y<4, and where z is the number of ether groups in the compound and is between 1 and 4, and where the ether and/or amine groups can be exo- and/or endocyclic; and
(25) at least one hydrocarbon structures having both amine and carbonyl functional groups having the general formula CnH2n+2−2u−2v−w−2x−3y−2z(NH2)w(NH)x(N)y(O)z where n is 1 to 12, and where u is the number of cyclic rings in the structure and is between 0 and 4, and where v is the number of unsaturated bonds in the structure and is between 0 and n, and where w is the number of primary amine groups, x is the number of secondary amine groups, y is the number of tertiary amine groups, and where 1<w+x+y<4, and where z is the number of carbonyl groups in the compound and is between 1 and 4, and where the carbonyl groups can be aldehyde(s) and/or ketone(s), and where the carbonyl and/or amine groups can be exo- and/or endocyclic;
and.
depositing steps (b) and (c) are via a process selected from the group consisting of chemical vapor depositions (CVD) and plasma enhanced chemical vapor depositions (PECVD).

### Claim 2

(canceled)

### Claim 3 (depends on 1)

The process for forming an air gap in claim 1, wherein the at least one organic precursor is at least one member selected from the group consisting of alpha-terpinene, limonene, cyclohexane, 1,2,4-trimethylcyclohexane, 1,5-dimethyl-1,5-cyclooctadiene, camphene, adamantane, 1,3-butadiene, substituted dienes, decahydronaphthelene, 1,5-cyclooctadiene, cyclooctane, cyclooctene, norbornadiene, 5-Ethylidene-2-norbornene, cyclopentene oxide and cyclopentanone.

### Claim 4 (depends on 1)

The process for forming an air gap in claim 1, wherein the sacrificial layer and the composite layer are deposited together in one chemical vapor deposition (CVD) step, or in one plasma enhanced chemical vapor deposition (PECVD) step.

### Claim 5 (depends on 1)

The process for forming an air gap in claim 1, wherein the energy in the applying step (d) includes at least one selected from the group consisting of α-particles, β-particles, γ-rays, x-rays, high energy electron, electron beam, visible light, infrared light, microwave frequency, radio-frequency, plasma, and combinations thereof.

### Claim 6 (depends on 1)

The process for forming an air gap in claim 1, wherein the applying energy step (d) is performed under conditions selected from the group consisting of
(1) an ultraviolet light energy having a power in the range of 0 to 5000 W;
an atmospheric condition selected from the group consisting of inert, oxidizing and reducing;
a temperature in the range of ambient to 500° C.; and
an exposure time in the range of 0.01 minute to 12 hours; and
(2) a thermal energy;
a pressure in the range of 10 mtorr to the atmospheric pressure;
an atmospheric condition selected from the group consisting of inert, oxidizing and reducing;
a temperature in the range of ambient to 500° C.;
and an exposure time in the range of 0.01 minute to 12 hours.

### Claim 7 (depends on 1)

The process for forming an air gap in claim 1, further comprising of filling pores in the porous layer with a polymizable organic species which can be activated towards polymerization.

### Claim 8 (depends on 6)

The process for forming an air gap in claim 6, wherein the energy in the applying step (d) is the thermal energy.

### Claim 9

A process for forming an air gap, the process comprising:
(a) providing a substrate;
(b) depositing a polar solvent soluble metal oxide sacrificial layer with a metal precursor;
(c) depositing a composite layer with a porogen and at least one silica-containing precursor or organosilicate glass (OSG) precursor;
(d) applying energy to the substrate having the sacrificial layer and the composite layer to remove the porogen to form a porous layer;
(e) contacting the substrate having the sacrificial layer and the porous layer with a polar solvent, optionally with a surfactant, capable of diffusing through the porous layer to remove the sacrificial layer to form air gaps;
(f) patterning a layer selected from the group consisting of the sacrificial layer, the composite layer, the porous layer and combinations thereof; and
(g) optionally, repeating steps (a)-(f) at least one time for making multilevel structures;
wherein the deposition of a polar solvent soluble metal oxide sacrificial layer in (b) and the deposition of a composite layer in (c) are via a process selected from the group consisting of a chemical vapor deposition (CVD), plasma enhanced chemical vapor depositions (PECVD), spin-on coating, dip-coating and mist deposition.

### Claim 10 (depends on 9)

The process for forming an air gap in claim 9, wherein the polar solvent soluble metal precursor is a germanium (Ge) based precursor selected from the group consisting of tetramethyl germane, germane, tetramethoxy germanium and tetraethoxy germanium; or a boron (B) based precursor selected from the group consisting of trimethyl boron, trimethoxy borane, triethoxy borane and diborane; and the polar solvent soluble metal oxide sacrificial layer is a GeO2 layer or a B2O3 layer.

### Claim 11 (depends on 9)

The process for forming an air gap in claim 9, wherein the polar solvent in step (e) is selected from the group consisting of alcohols, ethers, heteroatom containing molecules, esters, ketones, aldehydes and mixtures thereof.

### Claim 12 (depends on 9)

The process for forming an air gap in claim 9, wherein the polar solvent in step (e) is water.

### Claim 13 (depends on 9)

The process for forming an air gap in claim 9, wherein the energy in the applying step (d) includes at least one selected from the group consisting of α-particles, β-particles, γ-rays, x-rays, high energy electron, electron beam, ultraviolet light, visible light, infrared light, microwave frequency, radio-frequency, thermal, plasma, and combinations thereof.

### Claim 14 (depends on 9)

The process for forming an air gap in claim 9, wherein the applying energy step (d) is performed under conditions selected from the group consisting of
(1) an ultraviolet light having a power in the range of 0 to 5000 W;
an atmospheric condition selected from the group consisting of inert, oxidizing and reducing;
a temperature in the range of ambient to 500° C.; and
an exposure time in the range of 0.01 minute to 12 hours; and
(2) a thermal energy;
a pressure in the range of 10 mtorr to the atmospheric pressure;
an atmospheric condition selected from the group consisting of inert, oxidizing and reducing;
a temperature in the range of ambient to 500° C.;
and an exposure time in the range of 0.01 minute to 12 hours.

### Claim 15 (depends on 9)

The process for forming an air gap in claim 9, further comprising of filling pores in the porous layer with a polymizable organic species which can be activated towards polymerization.

### Claim 16

A process for forming an air gap, the process comprising:
(a) providing a substrate;
(b) depositing a polar solvent soluble metal oxide sacrificial layer with a metal precursor;
(c) depositing a composite layer with a porogen that is the polar solvent soluble metal oxide in (b) and at least one silica-containing precursor or organosilicate glass (OSG) precursor;
(d) contacting the substrate having the sacrificial layer and the composite layer with a polar solvent, optionally with a surfactant to facilitate the diffusion of the polar solvent through the sacrificial layer and the composite layer, to remove the porogen to form a porous layer and to remove the sacrificial layer to form air gaps;
(e) patterning a layer selected from the group consisting of the sacrificial layer, the composite layer, the porous layer and combinations thereof; and
(f) optionally, repeating steps (a)-(e) at least one time for making multilevel structures; wherein the depositing steps (b) and (c) are processes selected from the group consisting of a chemical vapor deposition (CVD), (plasma enhanced chemical vapor depositions (PECVD), spin-on coating, dip-coating and mist deposition.

### Claim 17 (depends on 16)

The process for forming an air gap in claim 16, wherein the polar solvent soluble metal precursor is a germanium (Ge) based precursor selected from the group consisting of tetramethyl germane, germane, tetramethoxy germane and tetraethoxy germanium; or a boron (B) based precursor selected from the group consisting of trimethyl boron, trimethoxy borane, triethoxy borane and diborane; and the polar solvent soluble metal oxide sacrificial layer is a GeO2 layer or a B2O3 layer.

### Claim 18 (depends on 16)

The process for forming an air gap in claim 16, wherein the polar solvent in step (e) is selected from the group consisting of alcohols, ethers, heteroatom containing molecules, esters, ketones, aldehydes and mixtures thereof.

### Claim 19 (depends on 16)

The process for forming an air gap in claim 16, wherein the polar solvent in step (e) is water.

### Claim 20 (depends on 16)

The process for forming an air gap in claim 16, further comprising of filling pores in the porous layer with a polymizable organic species which can be activated towards polymerization.

### Claim 21 (depends on 1)

The process for forming an air gap in claim 1, further comprising steps of:
(e) patterning a layer selected from the group consisting of the sacrificial layer, the composite layer, the porous layer and combinations thereof; and
(f) repeating steps (a)-(e) at least one time for making multilevel structures.