# US 11,442,362 B2 · Additive manufacturing of architectured materials

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- Number: US 11,442,362 B2
- Document ID: US11442362B2
- Status: Granted
- Kind: B2
- Application number: 16/669,379
- Filed: 2019-10-30
- Published: 2020-03-05
- Granted: 2022-09-13
- Earliest claimed: 2016-09-28
- Assignees: California Institute of Technology
- Applicants: California Institute of Technology
- Inventors: Andrey Vyatskikh; Stephane J. Delalande; Julia R. Greer
- Web page: https://patentgrep.com/patent/US11442362B2

## CPC

- G03F 7/0042: {with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists (G03F7/075 takes precedence)}
- G03F 7/0037: {Production of three-dimensional images}
- G03F 7/0043: {Chalcogenides; Silicon, germanium, arsenic or derivatives thereof; Metals, oxides or alloys thereof (G03F7/0044 takes precedence)}
- G03F 7/027: Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds (G03F7/075 takes precedence)
- G03F 7/2053: {using a laser (ablative removal B41C)}
- G03F 7/40: Treatment after imagewise removal, e.g. baking
- B33Y 10/00: Processes of additive manufacturing
- G03F: PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR; (phototypographic composing devices B41B; photosensitive materials or processes for photographic purposes G03C; electrophotography, sensitive layers or processes therefor G03G)
- B33Y: ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING

## Abstract

This disclosure provides a scalable and reproducible process to create complex 3D metal materials with sub-micron features by applying lithographic methods to transparent metal- or inorganic-rich polymer resins.

## Claims

### Claim 1

A method for manufacturing a sub-micron architectural material, comprising
patterning a hybrid organic-inorganic polymer resin comprising photopolymerizable functional groups and having the general structure:
Mn+(—R′OC—R)n
where M is a metal, a metal ion, a metalloid, a metal alloy, a metal oxide, a metal nitride, an inorganic, an inorganic-organic hybrid and/or metal-inorganic composite material, wherein R is a C2-10 terminal alkene and R′ is N, O, F, S or Cl and wherein n is 1, 2, 3, 4, 5 or 6, in the presence of a photoinitiator using a single or two photon lithography technique to polymerize the polymer resin and generate the sub-micron architectural material having desired characteristic dimension of about 5 nm to 5 micron across.

### Claim 2 (depends on 1)

The method of claim 1, wherein the hybrid organic-inorganic polymer resin has the formula R—COR′-M2+-R′OC—R, wherein M is a divalent metal ion, alloy, or inorganic material, R is a C2-10 terminal alkene and R′ is N, O, F, S or Cl.

### Claim 3 (depends on 1)

The method of claim 1, wherein the metal ion is selected from the group consisting of Li+, Na+, K+, Rb+, Cs+, Be2+, Mg2+, Ca2+, Sr2+, Ba2+, Sc3+, Sc2+, Sc+, Y3+, Y2+, Y+, Ti4+, Ti3+, Ti2+, Zr4+, Zr3+, Zr2+, Hf4+, Hf3+, V5+, V4+, V3+, V2+, Nb5+, Nb4+, Nb3+, Nb2+, Ta5+, Ta4+, Ta3+, Ta2+, Cr6+, Cr5+, Cr4+, Cr3+, Cr2+, Cr+, Cr, Mo6+, Mo5+, Mo4+, Mo3+, Mo2+, Mo+, Mo, W6+, W5+, W4+, W3+, W2+, W+, W, Mn7+, Mn6+, Mn5+, Mn4+, Mn3+, Mn2+, Mn+, Re+, Re6+, Re5+, Re+, Re3+, Re2+, Re+, Re, Fe6+, Fe4+, Fe3+, Fe2+, Fe+, Fe, Ru8+, Ru7+, Ru6+, Ru4+, Ru3+, Ru2+, Os8+, Os7+, Os6+, Os5+, Os4+, Os3+, Os2+, Os+, Os, Co5+, Co4+, Co3+, Co2+, Co+, Rh6+, Rh5+, Rh4+, Rh3+, Rh2+, Rh+, Ir6+, Ir5+, Ir4+, Ir3+, Ir2+, Ir+, Ir, Ni3+, Ni2+, Ni+, Ni, Pd6+, Pd4+, Pd2+, Pd+, Pd, Pt6+, Pt5+, Pt4+, Pt3+, Pt2+, Pt+, Cu4+, Cu3+, Cu2+, Cu+, Ag3+, Ag2+, Ag+, Au5+, Au4+, Au3+, Au2+, Au+, Zn2+, Zn+, Zn, Cd2+, Cd+, Hg4+, Hg2+, Hg+, B3+, B2+, B+, Al3+, Al2+, Al+, Ga3+, Ga2+, Ga+, In3+, In2+, In1+, Tl3+, Tl+, Si4+, Si3+, Si2+, Si+, Ge4+, Ge3+, Ge2+, Ge+, Ge, Sn4+, Sn2+, Pb4+, Pb2+, As5+, As3+, As2+, As+, Sb5+, Sb3+, Bi5+, Bi3+, Te6+, Te5+, Te4+, Te2+, La3+, La2+, Ce4+, Ce3+, Ce2+, Pr4+, Pr3+, Pr2+, Nd3+, Nd2+, Sm3+, Sm2+, Eu3+, Eu2+, Gd3+, Gd2+, Gd+, Tb4+, Tb3+, Tb2+, Tb+, Db3+, Db2+, Ho3+, Er3+, Tm4+, Tm3+, Tm2+, Yb3+, Yb2+, Lu3+ and alloys of any of the foregoing.

### Claim 4 (depends on 1)

The method of claim 1, wherein the inorganic is a single or mixed oxide, carbide, nitride, silicate, boride of Ti, W, Si, Zr, Al, Y, Cr, Fe, Pb, Co, or a rare earth element.

### Claim 5 (depends on 4)

The method of claim 4, wherein the inorganic is selected from the group consisting of TiO2, AlO2, Al2O3, ZrO2, SiC, SiO2, SiC, CeO2, and ZnO.

### Claim 6 (depends on 1)

The method of claim 1, wherein the metal-inorganic composite comprises Au—Ni—TiO2, Ni—Co—TiO2, Ni—Zn—Al2O3, or Ni—B—TiO2.

### Claim 7 (depends on 1)

The method of claim 1, further comprising removing non-polymerized resin.

### Claim 8 (depends on 1)

The method of claim 1, further comprising pyrolizing the sub-micron architectural material to remove organic material.

### Claim 9 (depends on 8)

The method of claim 8, wherein the pyrolizing comprises a two-step pyrolysis technique to remove organic material followed by removing oxygen.

### Claim 10 (depends on 8)

The method of claim 8, wherein the sub-micron architectural material comprises a metal, a metalloid and/or an inorganic structure having a dimension across an axis of a metal, a metalloid and/or a inorganic strut, beam or joint of less than 1 micron.