# US 9,437,817 B2 · Insulator material for use in RRAM

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- Number: US 9,437,817 B2
- Document ID: US9437817B2
- Status: Granted
- Kind: B2
- Application number: 13/959,553
- Filed: 2013-08-05
- Published: 2014-02-06
- Granted: 2016-09-06
- Earliest claimed: 2012-08-06
- Assignees: Imec
- Applicants: Imec
- Inventors: Christoph Adelmann; Malgorzata Jurczak
- Web page: https://patentgrep.com/patent/US9437817B2

## CPC

- H10N 70/8836: {Complex metal oxides, e.g. perovskites, spinels}
- C01G 27/006: {Compounds containing hafnium, with or without oxygen or hydrogen, and containing two or more other elements}
- C08K 3/04: Carbon
- C08K 3/08: Metals
- C23C 16/32: Carbides
- C23C 16/40: Oxides
- C23C 16/405: {of refractory metals or yttrium}
- C23C 16/45529: {specially adapted for making a layer stack of alternating different compositions or gradient compositions}
- C23C 16/45531: {specially adapted for making ternary or higher compositions}
- H10N 70/023: {by chemical vapor deposition, e.g. MOCVD, ALD}
- H10N 70/826: {adapted for essentially vertical current flow, e.g. sandwich or pillar type devices}
- H10N: ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- C01G: COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F (metal hydrides {monoborane, diborane or addition complexes thereof} C01B6/00; salts of oxyacids of halogens C01B11/00; peroxides, salts or peroxyacids C01B15/00; thiosulfates, dithionites, polythionates C01B17/64; compounds containing selenium, or tellurium C01B19/00; binary compounds of nitrogen with metals C01B21/06; azides C01B21/08; {compounds containing nitrogen, other non-metals and metal C01B21/082}; metal amides C01B21/092; nitrites C01B21/50; {compounds of noble gases C01B23/0005}; phosphides C01B25/08; salts of oxyacids of phosphorus C01B25/16; carbides C01B32/90; compounds containing silicon C01B33/00; compounds containing boron C01B35/00; compounds having molecular sieve properties but not having base-exchange properties C01B37/00; compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites, C01B39/00; cyanides C01C3/08; salts of cyanamide C01C3/16; thiocyanates C01C3/20)
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- C23C: COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04)

## Abstract

The present disclosure relates generally to Hf-comprising materials for use in, for example, the insulator of a RRAM device, and to methods for making such materials. In one aspect, the disclosure provides a method for the manufacture of a layer of material over a substrate, said method including a) providing a substrate, and b) depositing a layer of material on said substrate via ALD at a temperature of from 250 to 500° C., said depositing step comprising: at least one HfX4 pulse, and at least one trimethyl-aluminum (TMA) pulse, wherein X is a halogen selected from Cl, Br, I and F and is preferably Cl.

## Claims

### Claim 1

A method for the manufacture of a layer of material over a substrate, said method comprising:
a) providing a substrate, and
b) depositing a layer of material on said substrate via atomic layer deposition (ALD) at a temperature of from 250 to 500° C., said depositing step comprising one or more deposition cycles, each said deposition cycle comprising:
at least one HfX4 pulse followed by a purge, and
at least one trimethyl-aluminum (TMA) pulse followed by a purge, and
a single oxidizer (Ox) pulse followed by a purge,
wherein X is a halogen selected from Cl, Br and I, and
wherein a HfX4 pulse-purge sequence of each said deposition cycle is performed immediately before or immediately after a TMA pulse-purge sequence.

### Claim 2 (depends on 1)

The method according to claim 1, wherein in each said deposition cycle, at least one of the HfX4 pulse-purge sequences is immediately followed by one of the TMA pulse-purge sequences.

### Claim 3 (depends on 1)

The method according to claim 1, wherein said single Ox pulse is selected from H2O and O3 pulses.

### Claim 4 (depends on 1)

The method according to claim 1, wherein each said deposition cycle comprises a sequence of pulses HfX4/TMA/Oxidizer/.

### Claim 5 (depends on 1)

The method according to claim 1, further comprising a step of providing a HfO2 layer over or under said layer of material.

### Claim 6 (depends on 5)

The method according to claim 5, wherein said HfO2 layer is provided by a sequence of m cycles of pulses HfX4/Oxidizer/, wherein m is from 1 to 100.

### Claim 7 (depends on 1)

The method according to claim 1, wherein X is Cl.

### Claim 8 (depends on 1)

The method according to claim 1, wherein said temperature is from 300 to 400° C.

### Claim 9 (depends on 1)

The method according to claim 1, wherein the layer of material comprises the elements Hf, Al, O, and optionally C and X, wherein said elements Hf, Al, C, O and X make up at least 90 atom percent (at %) composition of the layer of material as determined by XPS, and wherein
Hf represents from 17 to 23% of the total at % of said elements Hf, Al, C, O and X as measured by XPS;
Al represents from 16 to 23% of the total at % of said elements Hf, Al, C, O and X as measured by XPS;
O represents 57 to 62% of the total at % of said elements Hf, Al, C, O and X as measured by XPS;
C represents from 0 to 3% of the total at % of said elements Hf, Al, C, O and X as measured by XPS; and
X represents from 0 to 1% of the total at % of said elements Hf, Al, C, O and X as measured by XPS.

### Claim 10 (depends on 9)

The method according to claim 9, wherein the layer of material comprises hydrogen atoms in an amount of 0-5 at % as measured by time-of-flight elastic recoil detection analysis.

### Claim 11 (depends on 1)

The method according to claim 1, wherein each said deposition cycle consists of a HfX4 pulse followed by a purge, a TMA pulse followed by purge, and an Ox pulse followed by a purge.

### Claim 12 (depends on 1)

The method according to claim 1, wherein each said deposition cycle consists of a sequence of pulses selected from the group consisting of:
HfX4/TMA/HfX4/Oxidizer/, and
HfX4/TMA/Oxidizer/.

### Claim 13 (depends on 1)

The method according to claim 1, wherein said depositing step comprises a plurality of deposition cycles, each said deposition cycle comprising a sequence of pulses HfX4/Oxidizer/TMA/.