# US 7,608,551 B2 · Bismuth containing fluorophosphate glass and method for making thereof

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- Number: US 7,608,551 B2
- Document ID: US7608551B2
- Status: Granted
- Kind: B2
- Application number: 11/174,862
- Filed: 2005-07-05
- Published: 2007-01-11
- Granted: 2009-10-27
- Earliest claimed: 2005-07-05
- Inventors: Alfred A. Margaryan; Ashot A. Margaryan
- Web page: https://patentgrep.com/patent/US7608551B2

## CPC

- C03B 5/08: Glass-melting pots
- C03C 3/247: containing fluorine and phosphorus
- C03C 4/0071: {for laserable glass}
- C03B: MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03C: CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS

## Abstract

New and improved compositions of doped and co-doped bismuth fluorophosphate glasses for lasers is disclosed that have a high refractive index (nD) of approximately 1.6 and higher, high transmission in the near infrared part of the spectrum, and a wide glass forming domain. The disclosed glass systems Al(PO3)3—Ba(PO3)2—Bi(PO3)3—BaF2+RFx+dopands use dopants from the group of oxides and or fluorides of rare earth elements Nd, Er, Yb, Tm, Tb, Ho, Sm, Eu and Pr as well as MnO and mixtures thereof over 100 percent (wt %) of the glass-base composition. These glasses have high chemical durability, radiation resistance, efficiency of laser use in the infrared and blue spectrum, and improved duration of luminescence.

## Claims

### Claim 1

A bismuth fluorophosphate glass formed from a composition comprising on a mol basis:
a metaphosphate Al(PO3)3, from 5 to 10 percent;
a metaphosphate Ba(PO3)2, from 8 to 13 percent;
a metaphosphate Bi(PO3)3, from 8 to 13 percent;
fluorides BaF2+RFx, from 64 to 79 percent; and
a rare earth dopant M2O3 or MF3 over 100 wt %;
where
R is selected from the group consisting of Ca, Mg, Pb, and Bi;
x is an index representing an amount of fluoride (F) in the compound RFx; and
M is selected from the group consisting of Lanthanide series.

### Claim 2 (depends on 1)

The bismuth fluorophosphate glass as set forth in claim 1, wherein the rare earth dopant M2O3 or MF3 over 100 wt %, are at 0.5 to 20 wt percent, with M selected from the group consisting of:
neodymium (Nd), erbium (Er), ytterbium (Yb), thulium (Tm), terbium (Tb), holmium (Ho), samarium (Sm), europium (Eu), praseodymium (Pr); and mixtures thereof.

### Claim 3

A bismuth fluorophosphate glass formed from a composition comprising on a mol basis:
a metaphosphate Al(PO3)3, from 4.5 to 5 percent;
a metaphosphate Ba(PO3)2, from 0.5 to 5 percent;
a metaphosphate Bi(PO3)3, from 16 to 94 percent;
fluorides BaF2+RFx, from 0.5 to 79 percent; and
a dopant over 100 wt % comprised of M2O3 or MF3 at 0.5 to 20 wt percent, with M selected from a group consisting of rare earth elements:
neodymium (Nd), erbium (Er), ytterbium (Yb), thulium (Tm), terbium (Tb), holmium (Ho), samarium (Sm), europium (Eu), praseodymium (Pr); and mixtures thereof;
where
R is selected from the group consisting of Ca, Mg, Pb, and Bi; and
x is an index representing an amount of fluoride (F) in the compound RFx.

### Claim 4

A bismuth fluorophosphate glass formed from a composition comprising on a mol basis:
a metaphosphate Al(PO3)3, from 10.5 to 11 percent;
a metaphosphate Ba(PO3)2, from 10 to 10.5 percent;
a metaphosphate Bi(PO3)3, from 0.5 to 78 percent;
fluorides BaF2+RFx, from 0.5 to 79 percent; and
dopant over 100 wt % comprised of M2O3 or MF3 at 0.5 to 20 percent, with M selected from a group consisting of rare earth elements:
neodymium (Nd), erbium (Er), ytterbium (Yb), thulium (Tm), terbium (Tb), holmium (Ho), samarium (Sm), europium (Eu), praseodymium (Pr); and mixtures thereof;
where
R is selected from the group consisting of Ca, Mg, Pb, and Bi; and
x is an index representing an amount of fluoride (F) in the compound RFx.

### Claim 5

A bismuth fluorophosphate glass formed from a composition comprising on a mol basis:
a metaphosphate Al(PO3)3, approximately 10.5 to 11 percent;
a metaphosphate Ba(PO3)2, approximately 0.5 to 78 percent;
a metaphosphate Bi(PO3)3, approximately 10 to 10.5 percent;
fluorides BaF2+RFx, approximately 0.5 to 79 percent; and
dopant over 100%, comprised of approximately 2 to 5 wt percent of oxide of neodymium (Nd);
where R is selected from the group consisting of Ca, Mg, Pb, and Bi; and
x is an index representing an amount of fluoride (F) in the compound RFx.

### Claim 6

A bismuth fluorophosphate glass formed from a composition comprising on a mol basis:
a metaphosphate Al(PO3)3, approximately 0.5 to 5 percent;
a metaphosphate Ba(PO3)2, approximately 16 to 94 percent;
a metaphosphate Bi(PO3)3, approximately 4.5 to 5 percent;
fluorides BaF2+RFx, approximately 0.5 to 79 percent; and
dopant over 100%, comprised of approximately 2 to 5 wt percent of oxide of erbium (Er);
where R is selected from the group consisting of Ca, Mg, Pb, and Bi; and
x is an index representing an amount of fluoride (F) in the compound RFx.

### Claim 7

A bismuth fluorophosphate glass formed from a composition comprising on a mol basis:
a metaphosphate Al(PO3)3, approximately 0.5 to 78 percent;
a metaphosphate Ba(PO3)2, approximately 10 to 10.5 percent;
a metaphosphate Bi(PO3)3, approximately 10.5 to 11 percent;
fluorides BaF2+RFx approximately 0.5 to 79 percent; and
a dopant over 100%, approximately 0.5 to 5 wt percent comprised of M2O3 or MF3, with M selected from a group consisting of rare earth elements:
neodymium (Nd), erbium (Er), ytterbium (Yb), thulium (Tm), terbium (Tb), holmium (Ho), samarium (Sm), europium (Eu), praseodymium (Pr); and mixtures thereof;
where R is selected from the group consisting of Ca, Mg, Pb, and Bi;
x is an index representing an amount of fluoride (F) in the compound RFx, forming fluorides selected from the group consisting of CaF2, MgF2, PbF2, and BiF3.

### Claim 8

A bismuth fluorophosphate glass formed from a composition comprising on a mol basis:
a metaphosphate Al(PO3)3, approximately 16.5 to 94 percent;
a metaphosphate Ba(PO3)2, approximately 0.5 to 5 percent;
a metaphosphate Bi(PO3)3, approximately 4 to 5 percent;
fluorides BaF2+RFx, approximately 0.5 to 79 percent; and
a dopant over 100%, approximately 0.5 to 10 wt percent of M2O3 or MF3, with M selected from a group consisting of rare earth elements:
neodymium (Nd), erbium (Er), ytterbium (Yb), thulium (Tm), terbium (Tb), holmium (Ho), samarium (Sm), europium (Eu), praseodymium (Pr); and mixtures thereof;
where R is selected from the group consisting of Ca, Mg, Pb, and Bi;
x is an index representing an amount of fluoride (F) in the compound RFx, forming fluorides selected from the group consisting of CaF2, MgF2, PbF2, and BiF3.

### Claim 9 (depends on 3)

The bismuth fluorophosphate glass as set forth in claim 3, further comprising a dopant comprised of an oxide of Mn over 100 wt % from 0.5 to 20 wt percent.

### Claim 10 (depends on 3)

The bismuth fluorophosphate glass as set forth in claim 3, further comprising a dopant comprised of an oxide of Mn over 100 wt % from 0.5 to 20 wt percent.

### Claim 11 (depends on 4)

The bismuth fluorophosphate glass as set forth in claim 4, further comprising a dopant comprised of an oxide of Mn over 100 wt % from 0.5 to 20 wt percent.

### Claim 12 (depends on 7)

The bismuth fluorophosphate glass as set forth in claim 7, further comprising a dopant comprised of an oxide of Mn over 100 wt % from 0.5 to 5 wt percent.

### Claim 13 (depends on 8)

The bismuth fluorophosphate glass as set forth in claim 8, further comprising a dopant comprised of an oxide of Mn over 100 wt % from 0.5 to 10 wt percent.