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US 20080304312A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2008/0304312 A1 Ho et al. (43) Pub. Date: Dec. 1 1, 2008 (54) RESISTANCE MEMORY WITH TUNGSTEN Publication Classi?cation COMPOUND AND MANUFACTURING (51) Int. Cl. (75) Inventors: ChiaHua Ho, Kaoshing City (TW); G11 C 11/ 00 (200601) Erh-Kun Lai, Longjing Shiang H05H 1/24 (200601) (TW) (52) US. Cl. ....................................... .. 365/148; 427/569 Correspondence Address: MACRONIX (57) ABSTRACT C/O HAYNES BEFFEL & WOLFELD LLP 1)_ ()_ BOX 366 Memory devices based on tungsten-oxide memory regions HALF MOON BAY, C A 94019 (Us) are described, along With methods for manufacturing and methods for programming such devices. The tungsten-oxide (73) Assignee: MACRONIX INTERNATIONAL memory region can be formed by oxidation of tungsten mate CO., LTD., HSINCHU (TW) rial using a non-critical mask, or even no mask at all in some embodiments. A memory device described herein includes a (21) APP1- NO-3 11/ 955,137 bottom electrode and a memory element on the bottom elec _ trode. The memory element comprises at least one tungsten (22) Flled: Dec‘ 12’ 2007 oxygen compound and is programmable to at least tWo resis Related U-s- Application Data tance states. A top electrode comprising a barrier material 1s on the memory element, the barrier material preventing (60) Provisional application No. 60/943,300, ?led on Jun. movement Of metal-ions frOm the top electrode intO the 11, 2007. memory element. i282 £2133 i284 /2114a 2210 2230 2240, \ \ \ é _ _ X x X < X X X -_-_- >< X X X X X X X X X X X X < X X X X . X X X X X X X X X X Z X < X X X X X ‘X X X X X X X X X X X X X X X X X X X X X X X " X X X I X X X X X X X X X >h X X X 2) X X X X X < X X X /< ’X J X X’. X X \T‘. - . / 2112b 2112c L/ {2221 2110b 2220 / 2290

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Page 1: i282 £2133 i284

US 20080304312A1

(19) United States (12) Patent Application Publication (10) Pub. No.: US 2008/0304312 A1

Ho et al. (43) Pub. Date: Dec. 1 1, 2008

(54) RESISTANCE MEMORY WITH TUNGSTEN Publication Classi?cation COMPOUND AND MANUFACTURING

(51) Int. Cl. (75) Inventors: ChiaHua Ho, Kaoshing City (TW); G11 C 11/ 00 (200601)

Erh-Kun Lai, Longjing Shiang H05H 1/24 (200601)

(TW) (52) US. Cl. ....................................... .. 365/148; 427/569

Correspondence Address: MACRONIX (57) ABSTRACT C/O HAYNES BEFFEL & WOLFELD LLP 1)_ ()_ BOX 366 Memory devices based on tungsten-oxide memory regions HALF MOON BAY, C A 94019 (Us) are described, along With methods for manufacturing and

methods for programming such devices. The tungsten-oxide (73) Assignee: MACRONIX INTERNATIONAL memory region can be formed by oxidation of tungsten mate

CO., LTD., HSINCHU (TW) rial using a non-critical mask, or even no mask at all in some embodiments. A memory device described herein includes a

(21) APP1- NO-3 11/ 955,137 bottom electrode and a memory element on the bottom elec _ trode. The memory element comprises at least one tungsten

(22) Flled: Dec‘ 12’ 2007 oxygen compound and is programmable to at least tWo resis

Related U-s- Application Data tance states. A top electrode comprising a barrier material 1s on the memory element, the barrier material preventing

(60) Provisional application No. 60/943,300, ?led on Jun. movement Of metal-ions frOm the top electrode intO the 11, 2007. memory element.

i282 £2133 i284

/2114a 2210 2230 2240, \ \ \ é _ _

X x X < X X X -_-_- >< X X X X X X X X X

X X X < X X X X . X X X X X X X X X X

Z X < X X X X ’ X ‘X X X X X X X

X X X X X X X X X X X X X X X X

" X X X I X X X X X X X X X

>h X X X 2) X X X X X < X X X

/< ’X J X X’. X X

\T‘. - . / 2112b 2112c —

L/

{2221 2110b 2220

/ 2290

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Dec. 11,2008 Sheet 1 0f36 US zoos/0304312 A1

18

X %

111‘ FIG. 1A

22 (1s

11)

X X X X X X X X X X X X X X X X

m X X X X X X X X X X X X X X

(X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X

X X X X X X X X X X X X X X X X X X X X X X X X X X X X X

X X X X X X X l X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X

X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X

_ i 5 4 q

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X X X X X X X X X X X X X X

X X X X X X X X X X X X X X X

FIG. 1D

\\

FIG. 1C

2 X v X X X X X X X X X X X X

I v X X X X X X X X X X X

X X X X X X X X X X X X

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:r Av

Patent Application Publication

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Patent Application Publication Dec. 11, 2008 Sheet 2 0f 36 US 2008/0304312 A1

sis ‘53's ' 5351“ 53'2 ' ss'u ' 555 I112‘! 1'1 's's' 3'2 2 BindinqEnergyieV] Binding EnergyEeV

DID G | |

Relative Fiatin ['15]

FIG. 3

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Patent Application Publication Dec. 11, 2008 Sheet 3 0f 36 US 2008/0304312 A1

0.04

Current (mA)

FIG. 4 0

I IIIIIII

Resistance (£2)

FIG. 5 101

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Patent Application Publication Dec. 11, 2008 Sheet 4 0f 36 US 2008/0304312 A1

100E ,5!

U Q

10;- \EI-UIJEI--EI-——EIEI 5 15000 Baking

ResistivityiQ-cm) ‘ -|:|- Off State 5 —O— On State

0.1 .- ‘?g

bro-ooo-o 00 _ Dim-l lfi’llllllll ||||||||| Iii-“ml III-Hm I

6 10-1101 104 105 105 107 ' Baking Time (sec)

100E ,1,’

in 105- ~~~|:|'-_—|:|---"""|:|“'------|:|III

5 25-000 Baking ResistivityiQ-cm) ‘ -|:|- Off State

I —O- On State 01- foo

' §O,O—O—-—O _ _|_%/ | ||||||l | |||||||| | |||||||l | |||||||l |

FIG 7 10-1 101 104 105 106 107 ' Baking Time (sec)

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Patent Application Publication Dec. 11, 2008 Sheet 5 0f 36 US 2008/0304312 A1

- I _

- \ ~ ' v ‘I Q -

Norm. Resistance

Ratio

-—I3— ZOOmV stress —O— 400mV stress —A— tUUOmV stress

10-1

Stress Time (sec)

SET/RESET Resistance

Ratio

_v_ CW9 :10 _a— Cycie = 500

FIG. 9

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Patent Application Publication Dec. 11, 2008 Sheet 6 0f 36 US 2008/0304312 A1

In (J) (A/BmZ) _

O . .

FIG I 1 1 Temperature(|<)

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Patent Application Publication Dec. 11, 2008 Sheet 7 0f 36 US 2008/0304312 A1

HesistivitylQ-cm) 1? ': f —|:|—0ffState - —Q— OnState

0.1; _

10E- _

' —|:|—OffState

—O— 0n State

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Patent Application Publication Dec. 11, 2008 Sheet 8 0f 36 US 2008/0304312 A1

Oxygen Content __._-________._

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Patent Application Publication Dec. 11, 2008 Sheet 9 0f 36 US 2008/0304312 A1

105E E

104;- Z: I g ?

Hessiance?l) 1035- O 6 m 4

1 | 10 -

NumberofShots

E E5

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103 _' I _ M‘

dmtc?frm?mmmjq?m I. 101 - I I I -- I I I

100 0 50 O .

H G I Number of Shots

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Patent Application Publication Dec. 11, 2008 Sheet 10 0f 36 US 2008/0304312 A1

‘20W - (a)

(3) '-2U;=<1U4L — imam-PH,“ ' ' ‘ ' I '

:.. Voltage (V) 0.0

—5.0><10—3 -

(4) — | I I I I

2 0,0 I 0.2

I VoltaggW; ~02 0.0 0.2

Vultage {"J}

FIG. 16

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Dec. 11, 2008 Sheet 11 0f 36 US 2008/0304312 A1

2;?

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$55 5 E

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Patent Application Publication

Resistance (9] 103:

Initial

Resistance (9) 103

102

FIG. 19

Dec. 11, 2008 Sheet 12 0f 36 US 2008/0304312 A1

“01 U

102

101 Time (sec)

“01 U

III‘ I I Illllll I I Illllll

Initial i in

150°C Baking iime (his)

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Patent Application Publication Dec. 11, 2008 Sheet 13 0f 36 US 2008/0304312 A1

1 201i l UTHER ":"RY :

: zusaq : i DATAIN 20“ : I DATADUT 20" E 1 STATE MACHME I

SENSEAMPLIFIERSIDATAINSTHUCTUHES 3955i

; \ —2U67 i 2065 206' ; ADDRESS’ ~r COLUMN UECODER J 3:

—2064 I

! AHHAYUFMEMORYCELLS I ; = HOW ‘ HAVING A RESISTANCE : ; DECUDEH 2062 MEMOHYBASEDDN : : TUNGSTENCUMPUUNDS ;

2068" ‘~2061 L2060 E BIASINGAHRANGEMENT E . SUPPLYVULTAGES ;

------------------

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US 2008/0304312 A1

$32 2% 5E Emmi .Gw $253.65 25:5 m2: 22>

3%

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SE SE

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Dec. 11, 2008 Sheet 14 0f 36 Patent Application Publication

55.

22 IT

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2; $253 Emmmg 2% D73 Emmi Em

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Page 17: i282 £2133 i284

US 2008/0304312 A1

MN .2"

EN 2%

Patent Application Publication Dec. 11, 2008 Sheet 16 0f 36

VAVAVAVAVAVAVAVAVAVAVAVAVAVAVAVAVAVAVAVAVAVAVAAVA VAVAVAVAVAVAIVFkIFLFKI/PkIKI/PVAVAVAVAVAVAVAVAVA VAVAVAVAVAH_A,VA:VA:VA~,VA:VA:VA:VA:VAIY_VAVAVAVAXVAVAVAVA VAVAVAVAVAVA_VAVAVAVAVAVAVAVAVA_VAVAVAVAJXVAVAVAVA VA 3 VA VA VA_ VA VA VA VA VA VA VA VA VA_VA VA VA VA A VA \ VA VA VA VA VA VA VA A _A x x VA VA VA VA VA VA V_H VA VA VA VA VA VA VA VA

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EN EN gm \

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US 2008/0304312 A1 Dec. 11, 2008 Sheet 18 0f 36

wox x

xxx x 1

xxxx x XXXXXXXLXXX x X X x X XX X\

x x x x x xi x xxxxx xx xxxxxxxmxxx x 2% EN 5% NE

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Patent Application Publication

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Dec. 11, 2008 Sheet 19 0f 36

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FIG. 26

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