Synthesis and characterization of black phosphorus intercalation compounds

Sy~2thetic Metals,

18 ( 1 9 8 7 ) 5 5 9 -- 5 6 4

559

S Y N T H E S I S AND C H A R A C T E R I Z A T I O N OF B L A C K P H O S P H O R U S I N T E R C A L A T I O N C O M P O U N D S

T. N I S H I I Mitsubishi

Peterochemical

Y. M A R U Y A M A

I n s t i t u t e for M o l e c u l a r I.

Co. Ltd.,

Yokkaichi,

Mie

5]0

(Japan)

and T. INABE Science~

Okazaki,

Aichi

444

I n s t i t u t e of T e c h n o l o g y j

Muroran,

Hokkaido

(Japan)

SHIROTANI

Muroran

050

(Japan)

ABSTRACT Black

Phosphorus-Iodine

first time.

Favorable

i n t e r c a l a t i o n c o m p o u n d s h a v e been s y n t h e s i z e d for the.

reaction conditions

s t r u c t u r e s h a v e been r e v e a l e d .

for the s y n t h e s i s

and

intercalated

T e m p e r a t u r e d e p e n d e n c e of e l e c t r i c a l

c o n d u c t i v i t i e s of b l a c k p h o s p h o r u s s i n g l e c r y s t a l s s i g n i f i c a n t l y c h a n g e s after intercalation Moreover,

and

in some cases a m e t a l l i c

phase is r e a l i z e d down to

it is n o t e d that the c o n d u c t i o n b e h a v i o r is r a t h e r

atmosphere

in the reaction,

namely

sensitive

1.5 K. to the

a trace of moisture.

INTRODUCTION Black

Phosphorus

(Black P hereafter) d i s c o v e r e d

been k n o w n to be a l a y e r e d to h a v e

interesting propertiesj

transitions [5].

structure

(Fig.

m o d i f i c a t i o n of B l a c k

1914 [I [2

has and

structure

[4] or the A n d e r s o n

localization

P to an i n t e r c a l a t i o n c o m p o u n d is a

p o t e n t i a l l y p r o m i s i n g s t r a t e g y to r e a l i z e a m e t a l l i c normal

in

semiconductor

such as the p r e s s u r e - i n d u c e d

[3] and a n o m a l o u s s u p e r c o n d u c t i v i t y

A chemical

by B r i d g m a n

1) n a r r o w gap

phase

in B l a c k P under

pressure.

At the first trial,

we used a l k a l i m e t a l s

(potassium,

c e s i u m or lithium) as

the d o n o r - t y p e i n t e r c a l a n t s and in the case of c e s i u m new e n h a n c i n g of the e l e c t r i c a l

conductivity were recognized

layer s t r u c t u r e s and [6].

Very recently

a l m o s t one unit c h a r g e t r a n s f e r f r o m each c e s i u m a t o m to B l a c k d e m o n s t r a t e d by X-ray K ~ - e m i s s i o n so r e a c t i v e w i t h p h o s p h o r u s that intercalation without

0379-6779/87/$3.50

spoiling

spectroscopy

[7].

Alkali

it is r a t h e r d i f f i c u l t the o r i g i n a l

to get

layer structure,

P has been

metals

are, h o w e v e r ~

a homogeneous

more or less.

© Elsevier Sequoia/Printed in The Netherlands

560

C

BJ 2.

Fig.

i. P u c k e r e d

A next provided

layer

candidate more

structure

of iodine,

significant

of Black

P crystal.

an a c c e p t o r

and s y s t e m a t i c

type i n t e r c a l a n t , results.

favorable

reaction

conditions

compounds

together

w i t h the s t r u c t u r e m o d e l

weight-gain reaction

measurement.

metallic

temperatures

p h a s e is a l s o

of B l a c k

revealed

are d e s c r i b e d

here on the

P-Iodine

intercalation

t h r o u g h X-ray a n a l y s i s

conduction b e h a v i o r s

Electrical

and measurement

actualized

for the s y n t h e s i s

has r e c e n t l y

We report

with respect

and an e v i d e n c e

and

to the

for an

discussed.

EXPERIMENTAL Black growth

P single

technique

crystals

u s e d in this e x p e r i m e n t

under high pressure

[8].

Iodine

w e r e p r e p a r e d by the m e l t vapor

purified

by s u b l i m a t i o n

w i t h CaO and KI was d i r e c t l y

reacted with Black

P crystals

The r e a c t i o n

commonly

and the r e a c t i o n

time was a l m o s t

were selected during

at s e v e r a l

the r e a c t i o n

crystal

the ac p l a n e 1.5 K w i t h

the

The

from 25°C to I00°C.

use

P-Iodine

out w i t h a q u a r t z

Weight-gain balance

with a Rigaku Geiger-flex

The t e m p e r a t u r e

of B l a c k

dependence crystals

of a f o u r - p r o b e

was m e a s u r e d

measurements

vacuum

Model

of e l e c t r i c a l

vessel.

temperatures

system.

The

2027 X-ray

resistivities

along

from room temperature

to

method.

AND DISCUSSION

The a t o m i c Black

points carried

s t r u c t u r e was a n a l y z e d

diffractometer.

RESULTS

were

two weeks

in a g l a s s

ratios

of iodine

P at r o o m t e m p e r a t u r e

nearly

saturated

to p h o s p h o r u s

are p l o t t e d

composition

after

corresponding

against

to the w e i g h t - g a i n

the r e a c t i o n

two weeks

time

in Fig.

2.

is P14 I.

°0

0

i 100

i

i 300

t

i 500

i 700

T(hrs) Fig.

2. A w e i g h t - g a i n

vs.

reaction

time p r o f i l e

of B l a c k

P and iodine

vapor.

of

561

New systematic were observed reacted

with

iodine

tentatively While for

lines

days,

molecules they are

vapor

assigned

the r e a c t i o n

13

(marked

in Fig. 3) t o g e t h e r

in the X-ray d i f f r a c t i o n

at r o o m t e m p e r a t u r e

to a first

condition

b is a l i t t l e

stage

for about

namely

almost vertically

O40)

six months,

P lines

which are

and b : 11.6 ~.

TB.p. = 40°C and T I : 25°C In b o t h c a s e s , in e v e r y

to the normal

Black

P p o w d e r which was

structure

b - 10.3 ~ [9].

a bit w i t h respect

(020)

with original

of the B l a c k

intercalation

was different,

shorter,

c o u l d be a c c o m m o d a t e d inclined

pattern

iodine

interlayer

space if

of e a c h p h o s p h o r u s

layer•

(OeO)

I

,L

11|) (041)

I

I

I 3O

2O

Fig.

3. An X-ray

The r e l a t i v e prepared

I

diffraction

electrical

at v a r i o u s

Fig. 4.

Black

P and B l a c k

semiconductors.

crystals

of h i g h e r

conductor

between

(EA:

I 5O

pattern

of

P-Iodine

Moreover

B]ack

pattern

P-Iodine

as

like a m e t a l l l c

below

of the h i g h e s t

like B l a c k

2 ~°" o.. o-" o~

.//

,

o::. .. .

3 \ 2

I 200

1

I

Temperature

.

:.

0 300

T(K)

4.

(50 ° and 70°C) b e h a v e

. ...'"

, 0

......

80 K is not temperature

P itself.

4 ....""•'.~

6",,

......•:-.~

........t=...o.....
I 100

i

I 200

: 300

T(K)

dependence

of R(T)/R(290K)

of B l a c k

(T) in

P-Iodine

6 BP-12(IO0 " c)

///

Fig.

Black

5 BP-12 ( 5 0 " c)

(in AIR)

I

I 100

crystals,

crysta]s

4 BP-12 ( 2 5 " c)

•

,

P-Iodine

temperature

at 25°C may be c l a s s i f i e d

w i t h these

20

n-

00

against

80 and 296 K and the rise of r e s i s t a n c e s

a semiconductive

: :

powder.

of B l a c k

are p l o t t e d

temperatures

2 BP-12 ( 7 0 "c) 3 BP-b

P-Iodine

R(T)/R(290K),

prepared

1 BLACK P 60

Black

temperatures

In c o n t r a s t

reaction

18--~5 meV).

C) shows again

I

resistancesj

reaction

impurity

steep

i 40

P-Iodine

systems.

so (100 °

562 We may a n a l y z e

these data

in terms of a c o n v e n t i o n a l

s e m i c o n d u c t o r physics

as

follows: (I) T < T I (minimum logarithms

resistance

of R(T)/R(290

point

we can get the d e p t h of a c c e p t o r with

EA,

the

low temperature

(2) T I < T < T 2 (maximum we can a s s u m e mobility

these

in T a b l e

K) a g a i n s t

the

I.

reaction

an

important

less.

higher

to T -3/2

TIME

BLACK P 25 o C, 50 o C, 70 o C, 80 o C, 100 0 C, 28 0 C,

12 DAYS 13 13 12 11 2 MONTHS

parameters,

temperatures

than

200 K).

In this

[10].

Taking

account

of the 2-

density.

R(4.2 K)/R(290 clearer,

in Fig.

for e l e c t r i c a l

K), EA, 6 , T I and T2,

we p l o t

\j

( meV

conductivity

)

18 14 5.5 5.4 5.1 8.9

52 25 4.0 1.8 1.7 7.1

TI

T2

(K)

(K)

X10 -2

55 54 67 80 50 62 20

238 238 280 290 275 262 300

1.4 1.4 4.0 6.0 2.8 2.7 4.6

~E

50

5. C h a r a c t e r i s t i c

100

T(°c)

T(°C)

parameters

vs.

reaction

temperatures

are

E A and R(4.2 K)/R(290

5.

R(4.2 K) R(290 K)

0

Fig.

region,

and the

5

0

to

in this range s h o u l d be p r o p o r t i o n a l

level

To make s i t u a t i o n

EA

TEMP

So,

Together

parameter

are s a t u r a t e d w i t h e l e c t r o n s

P, the r e s i s t a n c e s

parameters

CONDITION

1o

range,

more or

I

Characteristic

>

point

levels

N A is a c c e p t o r

characteristic

summarized

TABLE

resistance

of B l a c k

In this I/T,

EA, f r o m these relations.

K) is a l s o

of the h o l e is p r o p o r t i o n a l

to T/@-~A (~ T/6) w h e r e

to

conductivity.

that the a c c e p t o r

dimensionality

50 - 80 K).

proportional

levels,

the ratio of R(4.2 K)/R(290

identify

All

around

K) are a l m o s t

profiles.

563

Froln t h e s e temperatures ana L y s i s

are

of

we

in

the

worthwhile, Fig.

data,

can

the

range

criterion

especially

6 shows

the

b~.]ow 50 K.

and

conductivity carrier

may

the

Black

80°C.

or low

For

these

the

linearly

values

in t h e

to a m e t a l l i c fewer

than

specimens,

with

limit

is

against

conductances

phase,

so c a l l ~ d

normal

metals

0 K.

contemned.

of rather

This

a weak

t o be

temperatur*:

temperature of

a further seems

conductivity

relative

almost

reaction

conduction

specimens

decrease

much

these

temperature

of

P,

effective

semiconductive

to f i n i t e

be due are

the most

50 0 to

conductances with

tend

denslties

from

so far as

int{~rca]at ion c o m p o u n d s

that

for m e t a l ] i c

relative

in c o n t r a s t

exponentially

conclude

type

metal

than of

in w h i c h

[ ] I ].

0.9

•-

if) v

0.7

BP-,, (80" c ) / / / / /

0.5

,/i

,~

• BLACK P m"

D

/o

0.3

"

o

1

•

o..~"BP-12 (70 °e)

0.1 0

•

0

[

"

•

•

10

I

I

20

30

40

50

T(K) Etg.

~'~. P , e ] a t i v e

Finally, r,~acted

we

with

should

iodine

~uJite m e t a l l i c w~)r~ d l s o

and

vapor

in

assigned

influenc~

of

r!sultl!~q

discuss

behavior

observed

t,.ntativ~ly ar

conductJvities

at

water

to

X-ray

a first

is] a i r

irl l o w e r

the

a funetiori

atmospheric

room

down

tho to

as

of

effect

temperature 20

K

(Fig.

diffra
may

be

temperature.

in a i r

4,

curve

responsible

the

for

reaction.

two

3).

pattern

structure,

on

New

of t h i s

and ~or

b -

months

A sam} l,. showed

systematic specimen

11.66

in(:reasing

~.

]]ties

whlch

In

catrl~.r

this

~ e <'<~s<,

d~ilsll lp:<

T].

ACKNOWLEDGEMEN'I'S We are

indebted

arlalysis.

Prof.

M.

to P r o f . Sato

stimulating

discussions.

the

Special

Research

the

Ministry

of

on

H. S u e m a t s u

and

Prof.

This the

Education,

A.

work

Property Science

and

Mr.

Y.

Morita

are

also

was of and

partly

a part

acknowledged

supported

Moleuclar Culture.

Ito f o r

of X - r a y for

thelr

by t h e G r a n t - i n - A i d

AssembliEs

(No.60104006)

for froll

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