# US 10,370,290 B2 · Passivation glasses for semiconductor devices

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- Number: US 10,370,290 B2
- Document ID: US10370290B2
- Status: Granted
- Kind: B2
- Application number: 16/075,796
- Filed: 2017-05-03
- Published: 2019-02-21
- Granted: 2019-08-06
- Earliest claimed: 2016-08-03
- Assignees: Ferro Corporation
- Applicants: Ferro Corporation
- Inventors: Srinivasan Sridharan; John J. Maloney; George E. Sakoske; Gregory R. Prinzbach; David Widlewski; Jackie Davis; Bradford Smith
- Web page: https://patentgrep.com/patent/US10370290B2

## CPC

- C03C 4/16: for dielectric glass
- C03C 3/062: with less than 40% silica by weight
- C03C 3/066: containing zinc
- C03C 3/072: containing boron
- C03C 3/108: containing boron
- C03C 8/04: containing zinc
- C03C 8/10: containing lead
- C03C 8/22: containing two or more distinct frits having different compositions
- C03C 8/24: Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
- H10P 14/68: Organic materials, e.g. photoresists
- H10W 74/137: {the encapsulations being directly on the semiconductor body (H10W74/134 takes precedence)}
- H10W 74/43: comprising oxides, nitrides or carbides, e.g. ceramics or glasses
- C03C 2204/00: Glasses, glazes or enamels with special properties
- C03C 2205/00: Compositions applicable for the manufacture of vitreous enamels or glazes
- 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
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
- H10W: GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10

## Abstract

A passivation glass coating composition is provided for forming a fired passivation glass layer on a semiconductor substrate having p-n junction. The passivation glass coating composition includes a glass component that is lead free, cadmium free, alkali metal oxides free, and colored transition metal oxides (i.e. metal oxides of V, Fe, Co, Ni, Cr, Cu, Mn) free. The glass component includes bismuth based glasses, and provides a firing temperature range of 500° C. to 900° C., and controlled devitrification. Once fired to a semiconductor device, the fired passivation glass layer provides exceptional device performance including no cracking of the fired passivation glass layer, excellent thermal expansion matching to silicon, good chemical resistance to acid and base, and improved device performance.

## Claims

### Claim 1

A semiconductor device including a semiconductor including a p-n junction, and a passivation glass layer fired on the semiconductor and covering a periphery of the p-n junction, wherein prior to firing, the passivation glass layer includes a glass component comprising:
5-56 mole % Bi2O3,
15-60 mole % ZnO,
0.1-43 mole % B2O3,
0.1-15 mole % Al2O3,
4-53 mole % SiO2, and
1.5-43 mole % total R2O3, wherein R represents trivalent ions selected from the group consisting of B3+, Al3+, La3+, Y3+, Ga3+, In3+, Sc3+, and lanthanide ions from Ce3+ to Lu3+, and excluding color producing transition metal ions of Mn3+, Fe3+, Cr3+, V3+, Co3+.

### Claim 2 (depends on 1)

The semiconductor device according to claim 1, wherein the glass component further includes:
0.1-16 mole % BaO, and
0.1-16 mole % MgO.

### Claim 3 (depends on 2)

The semiconductor device according to claim 2, wherein the glass component further includes:
0.1-16 mole % (CaO+SrO), and
(B2O3+SiO2)≤54 mole %.

### Claim 4 (depends on 1)

The semiconductor device according to claim 1, wherein the glass component further includes:
0.1-15 mole % La2O3, and
0.2-42 mole % (B2O3+Al2O3).

### Claim 5 (depends on 1)

The semiconductor device according to claim 1, wherein the glass component includes:
5-18 mole % Bi2O3,
21-45 mole % ZnO,
1.5-23 mole % B2O3,
0.1-12 mole % Al2O3,
1.5-36 mole % total R2O3, and
25-48 mole % SiO2.

### Claim 6 (depends on 1)

The semiconductor device according to claim 1, wherein the glass component is free of color producing transition metal ions of V, Fe, Co, Ni, Cr, Cu, and Mn.

### Claim 7 (depends on 6)

The semiconductor device according to claim 6, wherein the glass component further includes:
0.1-6 mole % BaO, and
0.1-12 mole % MgO.

### Claim 8 (depends on 1)

The semiconductor device according to claim 1, wherein the glass component includes:
5-15 mole % Bi2O3,
25-43 mole % ZnO,
0.1-10 mole % B2O3,
5-12 mole % Al2O3,
1.5-36 mole % total R2O3, and
30-48 mole % SiO2.

### Claim 9 (depends on 8)

The semiconductor device according to claim 8, wherein the glass component includes 0.1-5 mole % B2O3.

### Claim 10 (depends on 8)

The semiconductor device according to claim 8, wherein the glass component is free of color producing transition metal ions of V, Fe, Co, Ni, Cr, Cu, and Mn.

### Claim 11 (depends on 8)

The semiconductor device according to claim 8, wherein the glass component further includes:
0.1-2 mole % BaO, and
5-12 mole % MgO.

### Claim 12 (depends on 8)

The semiconductor device according to claim 8, wherein (B2O3+SiO2)≤54 mole %.

### Claim 13 (depends on 1)

The semiconductor device according to claim 1, wherein the glass component has the following ranges of molar ratios of oxides:
(B2O3+Al2O3)/SiO2=0.1 to 9.0;
(B2O3+Al2O3)/ZnO≤5.0; and
R2O3/SiO2=0.1-15.

### Claim 14 (depends on 13)

The semiconductor device according to claim 13, wherein the molar ratio of (B2O3+Al2O3)/ZnO is less than or equal to 3.0.

### Claim 15 (depends on 13)

The semiconductor device according to claim 13, wherein:
(B2O3+Al2O3)/SiO2=0.1 to 1.2;
(B2O3+Al2O3)/ZnO≤2.0; and
R2O3/SiO2=0.1-2.0.

### Claim 16 (depends on 1)

The semiconductor device according to claim 1, wherein the glass component comprises at least a first glass frit comprising 10-42 mole % B2O3, and a second glass frit including 0-10 mole % B2O3, such that the total amount of B2O3 in the glass component is within the range of 0.1-43 mole %.

### Claim 17 (depends on 1)

The semiconductor device according to claim 1, wherein the fired passivation glass layer includes non-zinc-borate crystals comprising: ZnAl2O4, Zn2SiO4, Mg2Al4Si5O18, Zn2Ti3O8, ZnTiO3, Al2SiO5, other zinc silicates, other zinc titanates, other silicon zirconates, other aluminum silicates, calcium silicates, or combinations thereof.

### Claim 18 (depends on 1)

The semiconductor device according to claim 1, wherein the glass component further comprises 0.1-5 mole % of TiO2, ZrO2, GeO2, CeO2, or combinations thereof.

### Claim 19

A method of passivating a p-n junction, including:
providing a coating composition including a glass component comprising prior to firing, 5-56 mole % Bi2O3, 15-60 mole % ZnO, 0.1-43 mole % B2O3, 0.1-15 mole % Al2O3, 4-53 mole % SiO2, and 1.5-43 mole % total R2O3, wherein R represents trivalent ions selected from the group consisting of B3+, Al3+, La3+, Y3+, Ga3+, In3+, Sc3+, and lanthanide ions from Ce3+ to Lu3+, and excluding color producing transition metal ions of Mn3+, Fe3+, Cr3+, V3+, Co3+;
applying the coating composition to a periphery of a p-n junction; and
firing the coating composition to thereby form a fired passivation glass layer on the periphery of the p-n junction.

### Claim 20 (depends on 19)

The method according to claim 19, wherein the glass component is a mixture of at least two glasses.