# US 10,312,435 B1 · Method for manufacturing high density magnetic tunnel junction devices using photolithographic VIAS and chemically guided block copolymer self assembly

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- Number: US 10,312,435 B1
- Document ID: US10312435B1
- Status: Granted
- Kind: B1
- Application number: 15/866,370
- Filed: 2018-01-09
- Granted: 2019-06-04
- Earliest claimed: 2018-01-09
- Assignees: Spin Memory, Inc.
- Applicants: Spin Memory, Inc.
- Inventors: Elizabeth A. Dobisz; Prachi Shrivastava
- Web page: https://patentgrep.com/patent/US10312435B1

## CPC

- H10N 50/01: Manufacture or treatment
- G11C 11/161: {details concerning the memory cell structure, e.g. the layers of the ferromagnetic memory cell}
- G11C 11/1675: {Writing or programming circuits or methods}
- H01B 3/447: {from acrylic compounds}
- H01B 3/448: {from other vinyl compounds}
- H10B 61/00: Magnetic memory devices, e.g. magnetoresistive RAM [MRAM] devices
- H10K 71/211: {by selective transformation of an existing layer}
- H10N 50/80: Constructional details
- H10P 14/60: of insulating materials
- H10P 14/68: Organic materials, e.g. photoresists
- H10P 76/2041: {Photolithographic processes}
- H10P 76/4085: {characterised by the processes involved to create the masks}
- H10P 76/4088: {Processes for improving the resolution of the masks}
- G11C 2211/5615: Multilevel magnetic memory cell using non-magnetic non-conducting interlayer, e.g. MTJ
- H10N: ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- G11C: STATIC STORES (semiconductor memory devices H10B)
- H01B: CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES (selection for magnetic properties H01F1/00; waveguides H01P {; printed circuits H05K})
- H10B: ELECTRONIC MEMORY DEVICES
- H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10

## Abstract

A method for manufacturing a magnetic random access memory array at a density greater than would be possible using photolithography. A hard mask material is deposited over a magnetic memory element material, and a chemical template layer such as brush or mat material is deposited over the hard mask. A mask structure is formed over the soluble polymer. The mask structure is configured with openings having a center to center spacing that is an integer multiple of a block copolymer material. The openings in the mask structure can be shrunk by depositing a spacer material. The chemical template layer is chemically patterned, such as by a quick plasma exposure and the mask is removed. A block copolymer material is then deposited over the chemical template and annealed to form block copolymer cylinders that are located over the patterned portions of the chemical template and between the patterned portions.

## Claims

### Claim 1

A method for high density pillar structures, the method comprising:
depositing a pillar element material;
depositing a hard mask layer over the pillar element material;
depositing a chemical template layer over the hard mask layer;
depositing a soluble polymer over the chemical template layer;
forming a mask structure over the soluble polymer, the mask having openings that are separated by a spacing that is an integer multiple of a natural period of a block copolymer;
depositing a spacer layer over the mask structure to shrink the size of the opening in the mask structure;
performing an etching to remove a portion of the spacer layer and expose a portion of the underlying chemical template layer;
performing a plasma exposure to chemically pattern the exposed portion of the chemical template layer;
removing the soluble polymer and layers there-over;
depositing a block copolymer; and
annealing the block copolymer to cause the block copolymer to self assemble into cylinders, the cylinders being located over patterned portions of the chemical template layer and also in areas between the patterned portions of the chemical template layer.

### Claim 2 (depends on 1)

The method as in claim 1, further comprising after annealing the block copolymer, using the cylinders as mask structures to form an array of pillars from the pillar element material.

### Claim 3 (depends on 1)

The method as in claim 1, wherein the pillar element material is a plurality of layers for making a magnetic random access memory element.

### Claim 4 (depends on 1)

The method as in claim 1, wherein the spacer material comprises SiOx or SiNx.

### Claim 5 (depends on 1)

The method as in claim 1, wherein the block copolymer material comprises polystyrene-b-methylmethacrylate.

### Claim 6 (depends on 1)

The method as in claim 1, wherein the etching is an anisotropic etching.

### Claim 7 (depends on 1)

The method as in claim 1, wherein forming the mask further comprises:
depositing a photoresist; and
photolithographically patterning the photoresist.

### Claim 8 (depends on 7)

The method as in claim 7 further comprising, after annealing the block copolymer:
performing a reactive ion etching to transfer the image of the cylinders onto the underlying hard mask layer; and
performing an ion milling to transfer the image of the hard mask layer onto the pillar element material.

### Claim 9 (depends on 1)

The method as in claim 1, further comprising, after annealing the block copolymer:
converting the cylinders into cylindrical etch mask structures;
performing a reactive ion etching to transfer the image of the cylindrical etch mask structures onto the underlying hard mask layer to form a patterned hard mask structure; and
performing an ion milling to transfer the image of the patterned hard mask structure onto the underlying pillar element layer.

### Claim 10 (depends on 9)

The method as in claim 9, wherein converting the cylinders into cylindrical etch mask structures further comprises infusing metal oxide into the cylinders.

### Claim 11 (depends on 9)

The method as in claim 9, wherein converting the cylinders into cylindrical etch mask structures further comprises exposing the cylinders to a metal vapor and exposing the cylinders to water vapor.

### Claim 12 (depends on 9)

The method as in claim 9, wherein converting the cylinders into cylindrical etch mask structures further comprises removing the cylinders to form cylindrical openings in the block copolymer;
and filling the cylindrical openings with an etch mask material.

### Claim 13 (depends on 9)

The method as in claim 9, wherein the cylinders are surrounded by a copolymer matrix, and wherein converting the cylinders into cylindrical etch mask structures further comprises:
performing an ultraviolet light exposure to cross link the copolymer matrix and break down the cylinders;
perform an etching to remove the cylinders, leaving cylindrical openings in the block copolymer matrix;
depositing an etch mask material into the cylindrical openings in the block copolymer matrix; and
performing an etching to remove the block copolymer matrix.

### Claim 14 (depends on 13)

The method as in claim 13, wherein depositing an etch mask material into the cylindrical openings in the block copolymer material further comprises coating with spin on glass.

### Claim 15 (depends on 13)

The method as in claim 13, wherein the etch mask material is deposited by one or more of plasma vapor deposition and atomic layer deposition.

### Claim 16

A method for manufacturing a high density array of magnetic memory elements, the method comprising:
depositing a memory element material;
depositing a chemical template material over the memory element material;
forming a mask structure over the chemical template material, the mask structure having openings with a center to center spacing that is substantially equal to a natural period of a block copolymer;
shrinking the openings in the mask structure;
patterning the chemical template layer;
depositing a block copolymer over the patterned chemical template layer; and
annealing block copolymer to form block copolymer cylinders over the patterned regions of the patterned chemical template and between patterned regions of the patterned chemical template.

### Claim 17 (depends on 16)

The method as in claim 16, further comprising converting the block copolymer cylinders into cylindrical etch resistant mask structures.

### Claim 18 (depends on 16)

The method as in claim 16, further comprising exposing the block copolymer cylinders to a metal vapor and a water vapor.

### Claim 19 (depends on 16)

The method as in claim 16 further comprising repeatedly exposing the block copolymer cylinders to metal vapor and water vapor.

### Claim 20 (depends on 16)

The method as in claim 16 further wherein the block copolymer cylinders are surrounded by a block copolymer matrix and further comprising:
removing the block copolymer cylinders, leaving cylindrical openings in the block copolymer matrix; and
depositing an etch resistant material into the cylindrical openings in the block copolymer matrix.