US-20260130143-A1 - METHODS OF DEPOSITING THERMALLY CONDUCTIVE POLYMERIC FILMS

Abstract

Methods of depositing thermally conductive polymeric films are described. Each of the methods include flowing a first precursor over a substrate; removing a first precursor effluent comprising the first precursor; flowing a second precursor over the substrate to react with the first precursor to form the polymeric film on the substrate; and removing a second precursor effluent comprising the second precursor. The methods may include performing a metal deposition process. The methods may include performing a post-treatment process, such as a heat treatment process.

Inventors

• Xinke WANG
• Mark Saly
• John Sudijono
• Vicknesh Sahmuganathan
• Feng Q. Liu
• Bhaskar Jyoti Bhuyan

Assignees

• APPLIED MATERIALS, INC.

Dates

Publication Date

20260507

Application Date

20241107

Claims (20)

1. 1 . A method of depositing a polymeric film, the method comprising: flowing a first precursor over a substrate, the first precursor having a general formula R 1 -(X) n , where R 1 comprises one or more of an alkyl group, an alkenyl group, an aryl or aromatic group, and a cycloalkyl group, (X) n comprises one or more of a hydroxide group, an aldehyde group, a ketone group, an acid group, an amino group, an isocyanate group, a thiocyanate group, and an acyl chloride group, and n is an integer in a range of from 1 to 6; removing a first precursor effluent comprising the first precursor; flowing a second precursor over the substrate to react with the first precursor to form the polymeric film on the substrate, the second precursor having a general formula R 2 -(Y) n , where R 2 comprises one or more of an alkyl group, an alkenyl group, an aryl or aromatic group, and a cycloalkyl group, (Y) n comprises one or more of a hydroxide group, an aldehyde group, a ketone group, an acid group, an amino group, an isocyanate group, a thiocyanate group, and an acyl chloride group, and n is an integer in a range of from 1 to 6; and removing a second precursor effluent comprising the second precursor.
2. 2 . The method of claim 1 , further comprising pre-treating the substrate prior to flowing the first precursor, pre-treating the substrate including a gas soaking process or a plasma treatment process.
3. 3 . The method of claim 1 , wherein the first precursor comprises one or more of terephthaldehyde, terephthaloyl chloride, 1,3,5-benzenetricarbonyl trichloride, hexamethylene chloride, pyromellitic dianhydride, 1,4-phenylene diisocyanate, or terephthalic acid.
4. 4 . The method of claim 1 , wherein the second precursor comprises one or more of phenylenediamine, ethylenediamine, hexamethylenediamine, tris(2-aminoethyl)amine, ethanolamine, ethylene glycol, or 4,4′-oxydianiline.
5. 5 . The method of claim 1 , further comprising performing a chemical vapor deposition (CVD) process cycle, the CVD process cycle including exposing the substrate to a co-flow of the first precursor and the second precursor.
6. 6 . The method of claim 1 , further comprising performing a metal deposition process.
7. 7 . The method of claim 6 , wherein the metal deposition process comprises a metal doping process, the metal doping process including doping the polymeric film with a third precursor comprising one or more of aluminum (Al), zinc (Zn), titanium (Ti), tantalum (Ta), tin (Sn), hafnium (Hf), zirconium (Zr), gold (Au), ruthenium (Ru), or tungsten (W).
8. 8 . The method of claim 6 , wherein the metal deposition process comprises a physical vapor deposition (PVD) process, the PVD process including sputtering a third precursor comprising one or more of aluminum (Al), zinc (Zn), titanium (Ti), tantalum (Ta), tin (Sn), hafnium (Hf), zirconium (Zr), gold (Au), ruthenium (Ru), or tungsten (W).
9. 9 . The method of claim 6 , wherein the metal deposition process comprises an atomic layer deposition (ALD) process, the ALD process including exposing the substrate to a third precursor comprising one or more of aluminum (Al), zinc (Zn), titanium (Ti), tantalum (Ta), tin (Sn), hafnium (Hf), zirconium (Zr), gold (Au), ruthenium (Ru), or tungsten (W), removing a third precursor effluent comprising the third precursor, exposing the substrate to a fourth precursor comprising one or more of water (H 2 O), ammonia (NH 3 ), or hydrazine (N 2 H 4 ), and removing a fourth precursor effluent comprising the fourth precursor to form a metallic film on the polymeric film.
10. 10 . The method of claim 6 , wherein the metal deposition process comprises a vapor phase infiltration (VPI) process, the VPI process including diffusing a third precursor comprising one or more of aluminum (Al), zinc (Zn), titanium (Ti), tantalum (Ta), tin (Sn), hafnium (Hf), zirconium (Zr), gold (Au), ruthenium (Ru), or tungsten (W) into the polymeric film to form an organic-inorganic hybrid composite film.
11. 11 . The method of claim 6 , performed at a temperature in a range of from 20° C. to 300° C.
12. 12 . The method of claim 1 , further comprising performing a heat treatment process, the heat treatment process including one of more of thermal annealing, lithography, focused ion beam, laser annealing, or nanoimprinting.
13. 13 . The method of claim 12 , wherein the heat treatment process comprises thermally annealing the polymeric film at a temperature greater than or equal to 100°C.
14. 14 . A method of depositing a polymeric film, the method comprising: pre-treating a substrate; flowing a first precursor over the substrate, the first precursor having a general formula R 1 -(X) n , where R 1 comprises one or more of an alkyl group, an alkenyl group, an aryl or aromatic group, and a cycloalkyl group, (X) n comprises one or more of a hydroxide group, an aldehyde group, a ketone group, an acid group, an amino group, an isocyanate group, a thiocyanate group, and an acyl chloride group, and n is an integer in a range of from 1 to 6; removing a first precursor effluent comprising the first precursor; flowing a second precursor over the substrate to react with the first precursor to form the polymeric film on the substrate, the second precursor having a general formula R 2 -(Y) n , where R 2 comprises one or more of an alkyl group, an alkenyl group, an aryl or aromatic group, and a cycloalkyl group, (Y) n comprises one or more of a hydroxide group, an aldehyde group, a ketone group, an acid group, an amino group, an isocyanate group, a thiocyanate group, and an acyl chloride group, and n is an integer in a range of from 1 to 6; removing a second precursor effluent comprising the second precursor; and performing a heat treatment process.
15. 15 . The method of claim 14 , wherein pre-treating the substrate including a gas soaking process or a plasma treatment process.
16. 16 . The method of claim 14 , wherein the heat treatment process including one of more of thermal annealing, lithography, focused ion beam, laser annealing, or nanoimprinting.
17. 17 . The method of claim 16 , wherein the heat treatment process comprises thermally annealing the polymeric film at a temperature greater than or equal to 100°C.
18. 18 . The method of claim 14 , wherein the first precursor comprises one or more of terephthaldehyde, terephthaloyl chloride, 1,3,5-benzenetricarbonyl trichloride, hexamethylene chloride, pyromellitic dianhydride, 1,4-phenylene diisocyanate, or terephthalic acid, and the second precursor comprises one or more of phenylenediamine, ethylenediamine, hexamethylenediamine, tris(2-aminoethyl)amine, ethanolamine, ethylene glycol, or 4,4′-oxydianiline.
19. 19 . The method of claim 14 , further comprising performing a chemical vapor deposition (CVD) process cycle, the CVD process cycle including exposing the substrate to a co-flow of the first precursor and the second precursor.
20. 20 . The method of claim 14 , further comprising performing a metal deposition process prior to performing the heat treatment process, the metal deposition process comprising one or more of: a metal doping process including doping the polymeric film with a third precursor comprising one or more of aluminum (Al), zinc (Zn), titanium (Ti), tantalum (Ta), tin (Sn), hafnium (Hf), zirconium (Zr), gold (Au), ruthenium (Ru), or tungsten (W); a physical vapor deposition (PVD) process including sputtering a third precursor comprising one or more of aluminum (Al), zinc (Zn), titanium (Ti), tantalum (Ta), tin (Sn), hafnium (Hf), zirconium (Zr), gold (Au), ruthenium (Ru), or tungsten (W); an atomic layer deposition (ALD) process including exposing the substrate to a third precursor comprising one or more of aluminum (Al), zinc (Zn), titanium (Ti), tantalum (Ta), tin (Sn), hafnium (Hf), zirconium (Zr), gold (Au), ruthenium (Ru), or tungsten (W), removing a third precursor effluent comprising the third precursor, exposing the substrate to a fourth precursor comprising one or more of water (H 2 O), ammonia (NH 3 ), or hydrazine (N 2 H 4 ), and removing a fourth precursor effluent comprising the fourth precursor to form a metallic film on the polymeric film; or a vapor phase infiltration (VPI) process including diffusing a third precursor comprising one or more of aluminum (Al), zinc (Zn), titanium (Ti), tantalum (Ta), tin (Sn), hafnium (Hf), zirconium (Zr), gold (Au), ruthenium (Ru), or tungsten (W) into the polymeric film to form an organic-inorganic hybrid composite film.

Description

TECHNICAL FIELD Embodiments of the disclosure relate to electronic devices and methods of manufacturing electronic devices. More particularly, embodiments of the disclosure are directed to methods of depositing thermally conductive polymeric films. BACKGROUND Generally, an integrated circuit (IC) refers to a set of electronic devices, e.g., transistors, formed on a small chip of semiconductor material, typically silicon. Typically, the IC includes one or more metallization layers having metal lines to connect the electronic devices of the IC to one another and to external connections. Typically, layers of dielectric material are placed between the metallization layers of the IC for insulation. Semiconductor processing is often guided by ever decreasing node sizes. As dimensions shrink, further challenges arise in many processing steps and structures. This is further complicated for polymeric materials, which are deposited by wet processes, such as spin-coating. Wet processes, however, cannot operate in vacuum environments, and spin-coated polymer materials have a low glass transition temperature (Tg) due to low crystallinity. Accordingly, new methods of depositing thermally conductive polymeric materials are needed. SUMMARY One or more embodiments of the disclosure are directed to methods of depositing polymeric films. In one or more embodiments, a method of depositing a polymeric film comprises: flowing a first precursor over a substrate, the first precursor having a general formula R1-(X)n, where R1 comprises one or more of an alkyl group, an alkenyl group, an aryl or aromatic group, and a cycloalkyl group, (X)n comprises one or more of a hydroxide group, an aldehyde group, a ketone group, an acid group, an amino group, an isocyanate group, a thiocyanate group, and an acyl chloride group, and n is an integer in a range of from 1 to 6; removing a first precursor effluent comprising the first precursor; flowing a second precursor over the substrate to react with the first precursor to form the polymeric film on the substrate, the second precursor having a general formula R2-(Y)n, where R2 comprises one or more of an alkyl group, an alkenyl group, an aryl or aromatic group, and a cycloalkyl group, (Y)n comprises one or more of a hydroxide group, an aldehyde group, a ketone group, an acid group, an amino group, an isocyanate group, a thiocyanate group, and an acyl chloride group, and n is an integer in a range of from 1 to 6; and removing a second precursor effluent comprising the second precursor. Additional embodiments of the disclosure are directed to methods of depositing polymeric films. In one or more embodiments, a method of depositing a polymeric film comprises: pre-treating a substrate; flowing a first precursor over the substrate, the first precursor having a general formula R1-(X)n, where R1 comprises one or more of an alkyl group, an alkenyl group, an aryl or aromatic group, and a cycloalkyl group, (X)n comprises one or more of a hydroxide group, an aldehyde group, a ketone group, an acid group, an amino group, an isocyanate group, a thiocyanate group, and an acyl chloride group, and n is an integer in a range of from 1 to 6; removing a first precursor effluent comprising the first precursor; flowing a second precursor over the substrate to react with the first precursor to form the polymeric film on the substrate, the second precursor having a general formula R2-(Y)n, where R2 comprises one or more of an alkyl group, an alkenyl group, an aryl or aromatic group, and a cycloalkyl group, (Y)n comprises one or more of a hydroxide group, an aldehyde group, a ketone group, an acid group, an amino group, an isocyanate group, a thiocyanate group, and an acyl chloride group, and n is an integer in a range of from 1 to 6; removing a second precursor effluent comprising the second precursor; and performing a heat treatment process. BRIEF DESCRIPTION OF THE DRAWINGS So that the manner in which the above recited features of the disclosure can be understood in detail, a more particular description of the disclosure, briefly summarized above, may be had by reference to embodiments, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only typical embodiments of the disclosure and are therefore not to be considered limiting of its scope, for the disclosure may admit to other equally effective embodiments. The embodiments described herein are illustrated by way of example and not limitation in the Figures of the accompanying drawings in which like references indicate similar elements. FIG. 1 illustrates a process flow diagram of a method in accordance with one or more embodiments of the disclosure; FIG. 2A illustrates a process flow diagram of a method in accordance with one or more embodiments of the disclosure; FIG. 2B illustrates a process flow diagram of a method in accordance with one or more embodiments of the disclosure; FIG. 2C illustrat