WO2002010312A1

WO2002010312A1 - Preparation of high emission efficiency alkaline earth metal thiogallate phosphors

Info

Publication number: WO2002010312A1
Application number: PCT/US2001/021114
Authority: WO
Inventors: Perry Niel Yocom; Diane Zaremba
Original assignee: Sarnoff Corporation
Priority date: 2000-08-02
Filing date: 2001-07-25
Publication date: 2002-02-07
Also published as: JP2004505167A; JP4374442B2; US6544438B2; EP1305379A1; EP1305379A4; US20020014614A1

Abstract

A method of forming high efficiency emission alkali metal activated gallium sulfide phosphors by including an excess of 1-7% of gallium. A solution of a soluble gallium salt is added to a sulfate percipitate of an alkali metal sulfate and firing in hydrogen sulfide atmosphere at temperatures up to about 900°C.

Description

PREPARATION OF HIGH EMISSION EFFICIENCY ALKALINE EARTH METAL THIOGALLATE PHOSPHORS

This application claims priority from Provisional

application Serial No. 60/222,678 filed August 2, 2000.

This invention relates to a method of preparing high emission efficiency thiogallate phosphors. More particularly,

this invention relates to a method of preparing high emission

efficiency alkaline earth metal thiogallate phosphors activated with europium.

BACKGROUND OF THE INVENTION

Alkaline earth metal thiogallate phosphors (MGa₂S4) activated with divalent europium, praseodymium, trivalent

cerium and mixtures thereof, have been disclosed by Peters et al, J. Electrochem. Soc . , Vol. 119, 1972, p230. These

phosphors were made by solid state reaction from the alkaline

earth sulfide, gallium sulfide and rare earth sulfides. They

emit in the green to yellow region of the spectrum. They have

good saturation properties, but their emission efficiency is low, at about 30% that of other sulfide phosphors. However,

high efficiency phosphors are required for field emission displays, projection television, and blue-violet diode laser

light sources.

Thus a method of preparing the above phosphors that results in an improvement of their emission efficiency would

be highly desirable.

SUMMARY OF THE INVENTION

We have found that activated alkaline earth metal

thiogallate phosphors having improved emission efficiency can

be made by intimately mixing their insoluble sulfate salt

precursors having a small particle size with gallium nitrate

solution, in amounts to produce a small excess of gallium. The

soluble salts are precipitated with sulfuric acid or ammonium

sulfate to form their corresponding insoluble sulfates. These

solids are then fired in hydrogen sulfide to form the

corresponding thiogallate sulfide phosphors.

DETAILED DESCRIPTION OF THE INVENTION

The present method includes the following steps.

A soluble alkali metal salt, as of strontium or calcium

nitrate, is dissolved in dilute nitric acid. The desired

amount of europium activator (1-6 mol percent) is added as a

soluble salt, such as its nitrate. Neutralization with

ammonium hydroxide produces a suspension of alkali metal

sulfate particles coated with europium hydroxide.

The following equation summarizes this step:

Sr(S0₄) + Eu(N0₃)₂ + NH₄OH - SrS0₄ ^• Eu(OH)₃ + NH₄OH Sulfuric acid or ammonium sulfate is added to precipitate

the corresponding insoluble alkali metal sulfate. The particle size of the resultant precipitate should be kept small. This

can be done by controlling the temperature and concentration

of the soluble salt solution and by diluting the solution with

an organic, miscible solvent, such as an alcohol.

A solution of an acid-soluble gallium salt, such as the

nitrate, is also made. This can be done by dissolving the

metal in nitric acid overnight. Since gallium oxide is very

difficult to convert to an oxide-free sulfide with hydrogen sulfide, the oxide starting material is not recommended.

The gallium nitrate is added to the europium hydroxide

coated alkaline earth sulfate in sufficient amount so as to

produce an excess of from about 0.1-7 percent by weight of

gallium sulfide in the final gallium sulfide product, as

Sr(S0₄) :Eu:2.01Ga(OH)₃

After combining these solutions and bringing the mixture

to a neutral pH with ammonia, or by carrying out a

precipitation of gallium using urea, a solid precipitates. The solid phosphor precursor is dried, ground, placed in a refractory boat, such as an alumina boat, and fired in hydrogen sulfide for about five hours in a tube furnace. Suitably the firing temperature is about 800°C. The sulfide

product obtained is shown below:

SrGa₂S₄:Eu:Ga₂S₄

To ensure uniformity of the product, the sulfide material

is ground to a powder and refired in hydrogen sulfide at 900°C for about two hours. The resultant strontium thiogallate phosphor has a particle size of about 8-10 microns. Its

emission efficiency was measured at 80-100 percent.

The resultant green emitting, high emission efficiency

phosphor should show a slight excess of gallium sulfide by means of x-ray analysis, in the range of about 0.5-7 %.

If an organic solvent, such as an alcohol or acetone is

added when the sulfate is precipitated, and firing is carried

out at a lower temperature, such as 780°C for five hours and 850°C for about four hours, the average particle size of the

product will be somewhat smaller, e.g., about 5-6 microns.

Thus the product particle size can be controlled as required

by the final use of the phosphor.

A like calcium gallium sulfide activated with Eu can be made in similar manner but substituting a calcium salt for the strontium salt. A mixed crystal phosphor of strontium and calcium can also be made. Cerium or praseodymium can be substituted, in whole or in part, for the europium activator.

Reducing the amount of gallium present (for example a 5

to 3% excess) reduces the particle size and sometimes the

relative efficiency of the SrGa₂S₄ phosphor.

For example, samples with a 5% excess gallium, fired at

900°C for two hours can have a relative efficiency range of

from about 66 to 100%, with a median particle size of about

8.59 to 9.41 microns.

A sample with 3% excess gallium, plus the addition of alcohol in the precipitation step and fired at 850°C for four

hours, can have a relative efficiency of about 82% and a

median particle size of about 3.63 microns.

The invention will be further described by means of the

following examples. However, the invention is not meant to be

limited to the details described therein.

In the Examples, all parts are by weight.

Example 1

A solution of gallium nitrate was prepared as follows:

57.45 parts of gallium were dissolved in 400 ml cone, nitric acid. The mixture was heated until brown fumes appeared, when

the heat was removed and the container covered. After standing

overnight, the resultant green solution was alternately heated and cooled until it turned yellow, and then clear. Deionized

water was added to form 1000 ml of solution.

Ammonium hydroxide (about 80 ml) was added slowly to

obtain a solution pH of about 2. Water was added to make up 1200 ml of the solution.

Europium oxide (2.815 parts) was solubilized in 400 ml of

dilute nitric acid. Strontium carbonate was added slowly,

adding more nitric acid if needed. 1.2 ml of a 0.01 M solution

of praseodymium oxide was also added, and water was added to

make up 600 ml of solution.

Ammonium sulfate (120 parts) was dissolved in 540 ml of

water to make up 600 ml of solution.

The ammonium sulfate solution was added with stirring to the strontium-europium-praseodymium nitrate solution. The

mixture was stirred for ten minutes, and acidified to a pH of

about 1.4. The gallium nitrate solution was added, and the pH

raised to 7 with ammonium hydroxide. The mixture was stirred

for two hours and allowed to stand overnight.

The supernatant solution was decanted and filtered and

the precipitate washed with acetone. The precipitate was re-

suspended in 2500 ml of acetone, stirring for 1 hour at 50°C, and then filtered. The re-suspension step was repeated, and the precipitate dried overnight at 55°C.

The precipitate was ground in a ball mill with 140 alumina balls %"x7/l6" in size in acetone and dried overnight.

182 Grams of material were obtained.

The ground precipitate was heated at a rate of 20°C/min to

800°C in hydrogen sulfide and held for five hours. The resulting green phosphor was re-ground and fired again, this

time at 900°C in hydrogen sulfide for two hours. The average

particle size was about 8-10 microns. A yield of 120 grams was

obtained.

The green-emitting phosphor had a relative efficiency of 100%. Example 2

57.45 Parts of gallium was warmed until it liquified and

was dissolved in 400 parts by volume of nitric acid. When

brown fumes were seen, it was removed from the heat, covered and let set overnight. A green solution was obtained which was

warmed and cooled until it turned yellow, and finally clear.

Deionized water was added to make a one liter solution.

Ammonium hydroxide (about 80 ml) was added to a pH of about 2, and water added to make up 1200 ml of solution.

Europium oxide was dissolved in 400 ml of dilute nitric acid. Strontium carbonate was added slowly, and then 1.2 ml of

0.01M praseodymium solution was added. Water was added to make

up 600 ml of solution. The pH should be about 0.02 to 0.2 and

was adjusted as required.

500 Ml of ethanol was added slowly.

50 Ml of sulfuric acid was diluted with 300 ml of deionized water. The dilute sulfuric acid was added to the

strontium-europium-praeseodymium solution and stirred for 10

minutes. The pH was adjusted as required to be about the same

as the gallium solution. The gallium solution was added. The pH was adjusted to 7, and ethyl alcohol was added to make up 3.5 liters. The mixture was stirred for two hours, let set overnight and filtered. The precipitate was washed with

acetone . The precipitate was re-suspended in 3500 ml of acetone by

stirring for one hour at 50°C. The solids were filtered and

dried overnight at 55°C.

The solids were then ground and ball milled in 2500 ml of

acetone including 140 alumina balls. The solids were filtered

and dried overnight at 55°.

The precipitate was fired at 780°C for five hours, and then at 850°C for four hours. The average particle size was smaller than that of Example 1, i.e., about 5-6 microns. Thus

the phosphor was somewhat less efficient, about 82%, but had a

smaller median particle size of about 4 microns.

Although the invention has been described in terms of

particular embodiments, one skilled in the art will well know how to change the ingredients and their relative amounts. Thus

the invention is only meant to be limited to the details

described in the following claims.

Claims

We Claim :

1. An activated alkaline earth metal thiogallate phosphor

having an excess of gallium of from 0.1 to 7 percent by weight

based on gallium sulfide.

2. A thiogallate phosphor according to claim 1 wherein said

alkaline earth is strontium.

3. A thiogallate phosphor according to claim 1 wherein said

alkaline earth is calcium.

4. A method of making a high emission efficiency alkali metal

thiogallate phosphor comprising

intimately mixing an alkali metal sulfate having a

particle size below about 10 microns coated with an activator

with gallium nitrate solution in an amount such that an excess

of gallium is present in the final phosphor product,

precipitating the activated alkali metal gallium sulfate,

and firing in the presence of hydrogen sulfide.

5. A method according to claim 4 wherein an excess of 1 to 7

percent by weight of gallium is present in the phosphor.

6. A method of making high emission efficiency thiogallate

phosphors comprising

a) forming an aqueous solution of a soluble alkali metal

salt; b) adding a sulfate to precipitate an alkali metal

sulfate;

c) re-suspending the sulfate in water;

d) adding 2-5 mol percent of the sulfate of a soluble

activator salt,

e) precipitating the activator salt onto the alkali metal

sulfate;

f) adding a 1 to 7 percent excess of a solution of a

soluble gallium salt to the precipitate,

g) neutralizing the solution to form a precipitate, and

h) firing the precipitate in hydrogen sulfide to form the

corresponding sulfide phosphor.

7. A method according to claim 6 wherein the alkali metal is

selected from the group consisting of strontium, calcium and

mixtures thereof.

8. A method according to claim 6 wherein the activator is

selected from the group consisting of europium, praseodymium

and cerium.

9. A method according to claim 6 wherein step h) is carried

out by heating at 800°C and then at 850°C.

10. a method according to claim 6 wherein step h) is carried

out by heating at 800°C and then at 900°C.