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US 2005.

0022861A1
(19) United States
(12) Patent Application Publication (10) Pub. No.: US 2005/0022861 A1
ROSe et al. (43) Pub. Date: Feb. 3, 2005
(54) ETCHING OF SOLAR CELL MATERIALS (52) U.S. Cl. .............................................. 136/256; 438/98
(76) Inventors: Douglas H. Rose, Austin, TX (US); (57) ABSTRACT
Pongsthorn Uralwong, Campbell, CA
(US); David D. Smith, San Jose, CA A Solar cell is fabricated by etching one or more of its layers
(US) without Substantially etching another layer of the Solar cell.
In one embodiment, a copper layer in the Solar cell is etched
Correspondence Address: without Substantially etching a topmost metallic layer com
OKAMOTO & BENEDICTO, LLP prising tin. For example, an etchant comprising Sulfuric acid
P.O. BOX 64.1330 and hydrogen peroxide may be employed to etch the copper
SAN JOSE, CA 95164 (US) layer Selective to the tin layer. A particular example of the
aforementioned etchant is a Co-Bra Etcho(E) etchant modi
(21) Appl. No.: 10/632,747 fied to comprise about 1% by volume of sulfuric acid, about
4% by volume of phosphoric acid, and about 2% by volume
(22) Filed: Aug. 1, 2003 of Stabilized hydrogen peroxide. In one embodiment, an
aluminum layer in the Solar cell is etched without Substan
Publication Classification tially etching the tin layer. For example, an etchant com
prising potassium hydroxide may be employed to etch the
(51) Int. Cl. .................................................. H01L 31/00 aluminum layer without Substantially etching the tin layer.

is:
Patent Application Publication Feb. 3, 2005 Sheet 1 of 3 US 2005/0022861 A1

:
Patent Application Publication Feb. 3, 2005 Sheet 2 of 3 US 2005/0022861 A1
Patent Application Publication Feb. 3, 2005 Sheet 3 of 3 US 2005/0022861 A1

500

504

on 506

508

51O

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514

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F.G. 5
US 2005/0022861 A1 Feb. 3, 2005

ETCHING OF SOLAR CELL MATERIALS rials, process Steps, and structures to provide a thorough
understanding of embodiments of the invention. Persons of
BACKGROUND OF THE INVENTION ordinary skill in the art will recognize, however, that the
0001) 1. Field of the Invention invention can be practiced without one or more of the
Specific details. In other instances, well-known details are
0002 The present invention relates generally to Solar not shown or described to avoid obscuring aspects of the
cells, and more particularly but not exclusively to Solar cell invention.
fabrication processes and Structures.
0010 FIGS. 1-4 show sectional views schematically
0.003 2. Description of the Background Art Solar cells illustrating the fabrication of a Solar cell in accordance with
are well known devices for converting Solar radiation to an embodiment of the present invention. FIGS. 1-4, which
electrical energy. They may be fabricated on a Semiconduc are not drawn to Scale, show the Solar cell in the middle of
tor wafer using Semiconductor processing technology. Gen the fabrication process. Masking Steps are not shown or
erally Speaking, a Solar cell may be fabricated by forming described in the interest of clarity.
p-doped and n-doped regions in a Silicon Substrate. Solar
radiation impinging on the Solar cell creates electrons and 0011. In FIG. 1, the Solar cell is shown as having a tin
holes that migrate to the p-doped and n-doped regions, (Sn) layer 112, a copper (Cu) layer 110, a copper layer 108,
thereby creating Voltage differentials between the doped a titanium-tungsten (TIW) layer 106, an aluminum (Al) layer
regions. The Side of the Solar cell where connections to an 104, a silicon dioxide (SiO) layer 102, and a silicon (Si)
external electrical circuit are made includes a topmost substrate 100. Tin layer 112 is on the backside of the solar
metallic Surface that is electrically coupled to the doped cell, while silicon Substrate 100 is towards the front or Sun
regions. There may be Several layers of materials between side. The Solar cell being fabricated is a so-called “backside
the metallic Surface and the doped regions. These materials contact Solar cell” in that all electrical connections to the
may be patterned and etched to form internal Structures. It is doped regions (not shown) in silicon substrate 100 are made
important to etch these materials in a way that would not from the backside of the solar cell by way of tin layer 112.
compromise the operability and performance of the Solar However, it is to be noted that the present invention is not
cell. limited to backside-contact Solar cells. The teachings of the
present disclosure may be employed in the fabrication of
SUMMARY Solar cells in general.
0004. A Solar cell is fabricated by etching one or more of 0012. In the example of FIG. 1, tin layer 112 is the
its layers without Substantially etching another layer of the topmost metallic layer and provides a Solderable metallic
Solar cell. In one embodiment, a copper layer in the Solar cell Surface on which electrical connections may be made. For
is etched without Substantially etching a topmost metallic example, interconnect leads coupled to an external electrical
layer comprising tin. For example, an etchant comprising circuit or other Solar cells may be soldered on tin layer 112.
Sulfuric acid and hydrogen peroxide may be employed to Tin layer 112 also protects underlying layers of materials.
etch the copper layer Selective to the tin layer. A particular For example, tin layer 112 helps prevent copper layer 110
example of the aforementioned etchant is a Co-Bra Etch(R) from corroding. In one embodiment, tin layer 112 is elec
etchant modified to comprise about 1% by volume of troplated to a thickness of about 5 microns on copper layer
Sulfuric acid, about 4% by Volume of phosphoric acid, and 110.
about 2% by volume of stabilized hydrogen peroxide. In one
embodiment, an aluminum layer in the Solar cell is etched 0013 Copper layer 110, copper layer 108, titanium
without Substantially etching the tin layer. For example, an tungsten layer 106, and aluminum layer 104 form a Cu/TW/
etchant comprising potassium hydroxide may be employed All metal Stack that provides electrical connectivity to doped
to etch the aluminum layer without Substantially etching the regions in Silicon Substrate 100. In one embodiment, copper
tin layer. layer 110 is electroplated to a thickness of about 20 microns
on copper layer 108. Masks (not shown) may be formed
0005 These and other features of the present invention between individual Structures of copper layer 110 in gaps
will be readily apparent to perSons of ordinary skill in the art 113 before the electroplating proceSS. The masks are
upon reading the entirety of this disclosure, which includes removed after the electroplating process to obtain the Struc
the accompanying drawings and claims. ture shown in FIG. 1.
DESCRIPTION OF THE DRAWINGS 0014 Copper layer 108 serves as a seed layer for the
0006 FIGS. 1-4 show sectional views schematically electroplating of copper layer 110. Copper layer 108 may be
illustrating the fabrication of a Solar cell in accordance with formed to a thickness of about 1600 Angstroms by sputter
an embodiment of the present invention. ing. Titanium-tungsten layer 106 and aluminum layer 104
may also be formed by Sputtering. In one embodiment,
0007 FIG. 5 shows a flow diagram of a method of titanium-tungsten layer 106 and aluminum layer 104 are
etching one or more materials in a Solar cell in accordance each formed to a thickness of about 1000 Angstroms.
with an embodiment of the present invention. Aluminum layer 104 may comprise aluminum with 1%
0008. The use of the same reference label indifferent Silicon alloy.
drawings indicates the same or like components. 0015 Silicon dioxide layer 102 serves as a dielectric
DETAILED DESCRIPTION
layer providing electrical isolation between the Overlying
Cu/TW/Al metal stack and silicon Substrate 100. Vias are
0009. In the present disclosure, numerous specific details formed through silicon dioxide layer 102 in sections where
are provided Such as examples of process parameters, mate the Cu/TW/Al metal stack makes contact with the doped
US 2005/0022861 A1 Feb. 3, 2005

regions in silicon Substrate 100. In one embodiment, silicon minutes at 40°C. About 1000 Angstroms of aluminum layer
dioxide layer 102 is formed to a thickness of about 950 104 were removed without excessively etching tin layer 112,
Angstroms. copper layers 110 and 108, titanium-tungsten layer 106, and
silicon dioxide layer 102.
0016. There may be steps in the fabrication of a Solar cell 0021. The teachings of the present disclosure may be
where an etch is performed through a Stack of materials
comprising copper, titanium-tungsten, and aluminum. To generally employed to etch one or more layers of materials
prevent damaging the Solar cell, each layer in the material in a Solar cell being fabricated. For example, the etching
Stack may need to be etched without attacking (i.e., exces techniques disclosed herein may be employed in the fabri
Sively etching) other layers of the Solar cell. In the example cation of Solar cells disclosed in the following commonly
of FIG. 1, copper layer 108, titanium-tungsten layer 106, assigned disclosures, which are incorporated herein by ref
and aluminum layer 104 need to be etched without attacking erence in their entirety: U.S. application Ser. No. 10/412,
tin layer 112. Excessive etching of tin layer 112 may 638, entitled “Improved Solar Cell and Method of
compromise its ability to protect the underlying metal Stack. Manufacture,” filed on Apr. 10, 2003 by William P. Mulli
gan, Michael J. Cudzinovic, Thomas Pass, David Smith,
0.017. One way of etching through copper layer 108, Neil Kaminar, Keith McIntosh, and Richard M. Swanson;
titanium-tungsten layer 106, and aluminum layer 104 is to and U.S. application Ser. No. 10/412,711, entitled “Metal
use a so-called “PAWN” (phosphoric, acetic, water, nitric) Contact Structure For Solar Cell And Method Of Manufac
solution to etch copper layer 108 and aluminum layer 104. ture,” filed on Apr. 10, 2003 by William P. Mulligan,
For example, the sample of FIG. 1 may be wet etched in a Michael J. Cudzinovic, Thomas Pass, David Smith, and
PAWN bath to etch copper layer 108, in a hydrogen peroxide Richard M. Swanson. It is to be noted, however, that the
bath to etch titanium-tungsten layer 106, and in a PAWN aforementioned disclosures are referenced herein only as
bath to etch aluminum layer 104. PAWN is commonly used examples.
to etch aluminum in the electronics industry, which does not
require Selectivity to copper, tin, and other materials 0022. The etch chemistries provided herein not only
employed in Solar cells. The inventors found that PAWN has allow Selectivity to materials found in Solar cells, but also
a tendency to attack tin layer 112 during the etching of have relatively high etch capacity, are cost-effective, and are
copper layer 108 and aluminum layer 104. The present easily replenished and controlled. Embodiments, of the
disclosure provides improved techniques for etching a cop present invention may thus be advantageously employed to
per layer, a titanium-tungsten layer, and/or aluminum layer etch a single layer of material or a Stack of materials in Solar
without Substantially etching a tin layer in a Solar cell or cell fabrication processes in general.
Similar device. The techniques may be employed to etch 0023 Referring now to FIG. 5, there is shown a flow
Several layers of a material Stack or a single layer. diagram of a method 500 of etching one or more materials
0018 Continuing in FIG. 2, copper layer 108 is etched in a Solar cell in accordance with an embodiment of the
selective to tin layer 112 and titanium-tungsten layer 106. present invention. Among its other uses, method 500 may be
Copper layer 108 may be wet etched in a solution compris employed to etch through a material Stack comprising cop
ing Sulfuric acid and hydrogen peroxide. For example, per, titanium-tungsten, and aluminum in a Solar cell. Method
copper layer 108 may be wet etched using a Co-Bra Etch(R) 500 will be described using FIGS. 1-4 as an example.
etchant modified to comprise about 1% by volume of 0024. In step 502 and with reference to FIG. 1, a plating
Sulfuric acid, about 4% by Volume of phosphoric acid, and mask, if any, that may have been employed in the electro
about 2% by volume of stabilized hydrogen peroxide. A plating of copper layer 110 is removed. Step 502 may be
Perma-Etch(R) etchant may also be employed to etch copper performed by placing the sample of FIG. 1 in about 2% to
layer 108. Co-Bra Etch(R) and Perma-Etch(R) etchants are 3% potassium hydroxide bath at 40 C. for about 5 minutes.
both commercially available from Electrochemicals, Inc. of
Maple Plain, Minn. In one experiment, a Sample Similar to 0025. In step 504, the sample of FIG. 1 is rinsed. For
that shown in FIG. 1 was dipped in a bath of the aforemen example, the sample of FIG. 1 may be placed in a bath of
tioned modified Co-Bra Etch(R) etchant for about 1 minute at deionized water, Spray-rinsed with deionized water, and then
40° C. About 1600 Angstroms of copper layer 108 were dumped-rinsed in deionized water.
removed without excessively etching tin layer 112 or tita 0026. In step 506, copper layer 108 is etched as shown in
nium-tungsten layer 106. FIG. 2. Step 506 may be performed by placing the sample
0019. In FIG. 3, titanium-tungsten layer 106 is etched of FIG. 1 in a bath of a Co-Bra Etch(E) etchant modified to
selective to tin layer 112, copper layers 110 and 108, and comprise about 1% by volume of sulfuric acid, about 4% by
aluminum layer 104. Titanium-tungsten layer 106 may be volume of phosphoric acid, and about 2% by volume of
wet etched in a bath of hydrogen peroxide, for example. The stabilized hydrogen peroxide at 43 C. with robotic agitation
hydrogen peroxide may be 30% by weight (balance is for about 2 minutes and 10 seconds.
water). 0027. In step 508, the sample of FIG. 2 is rinsed. Step
0020. In FIG. 4, aluminum layer 104 is etched selective 508 may be performed by dump-rinsing the sample of FIG.
to tin layer 112, copper layers 110 and 108, titanium 2 in deionized water.
tungsten layer 106, and silicon dioxide layer 102. Aluminum 0028. In step 510, titanium-tungsten layer 106 is etched
layer 104 may be wet etched in a bath of potassium as shown in FIG. 3. Step 510 may be performed by placing
hydroxide. In one embodiment, aluminum layer 104 is wet the sample of FIG. 3 in a bath of about 30% by weight
etched using an etchant comprising about 1% by Volume of hydrogen peroxide at 40°C. with robotic agitation for about
potassium hydroxide in water. Other concentrations of 2 minutes and 15 Seconds.
potassium hydroxide may also be employed depending on
the application. In one experiment, a Sample similar to that 0029. In step 512, the sample of FIG. 3 is rinsed. Step
shown in FIG. 3 was dipped in a bath comprising about 1% 512 may be performed by dump-rinsing the sample of FIG.
by volume of potassium hydroxide in water for about 1.5 3 in deionized water.
US 2005/0022861 A1 Feb. 3, 2005

0.030. In step 514, aluminum layer 104 is etched as shown 14. The method of claim 13 wherein the etchant com
in FIG. 4. Step 514 may be performed by placing the sample prises about 1% by volume of sulfuric acid, about 4% by
of FIG. 3 in a bath of about 1% by volume potassium volume of phosphoric acid, and about 2% by volume of
hydroxide at 40 C. for about 2 minutes and 15 seconds. Stabilized hydrogen peroxide.
0031. In step 516, the sample of FIG. 4 is rinsed. Step 15. A method of etching a layer of material in a Solar cell,
516 may be performed by dump-rinsing the sample of FIG. the method comprising:
4 in deionized water. etching a metal layer without Substantially etching a tin
0032). In step 518, the sample of FIG. 4 is dried. Step 518 layer of a Solar cell.
may be performed by Spin-rinse drying. Air-knife and 16. The method of claim 15 wherein the metal layer
meniscus drying techniques may also be employed to dry the comprises copper.
sample of FIG. 4. 17. The method of claim 15 wherein the metal layer
comprises copper etched using an etchant comprising about
0.033 While specific embodiments of the present inven 1% by volume of Sulfuric acid, about 4% by volume of
tion have been provided, it is to be understood that these phosphoric acid, and about 2% by volume of stabilized
embodiments are for illustration purposes and not limiting. hydrogen peroxide.
For example, the above described etchants may also be 18. The method of claim 15 wherein the metal layer
applied using in-line drag-through and in-line Spray Systems. comprises copper etched using an etchant comprising hydro
Many additional embodiments will be apparent to perSons of gen peroxide and Sulfuric acid.
ordinary skill in the art reading this disclosure. 19. The method of claim 15 wherein the metal layer
What is claimed is: comprises aluminum.
1. A method of fabricating a Solar cell, the method 20. The method of claim 15 wherein the metal layer
comprising: comprises aluminum etched using an etchant comprising
potassium hydroxide.
etching a first layer comprising copper without Substan 21. The method of claim 15 wherein the metal layer
tially etching a topmost metallic layer of a Solar cell. comprises aluminum etched using an etchant comprising
2. The method of claim 1 wherein the topmost metallic about 1% by volume of potassium hydroxide in water.
layer comprises tin. 22. A method of etching a layer of material in a Solar cell,
3. The method of claim 1 wherein the first layer is etched the method comprising:
using an etchant comprising Sulfuric acid and hydrogen
peroxide. etching an aluminum layer Selective to a tin layer using an
4. The method of claim 1 wherein the first layer is etched etchant comprising potassium hydroxide.
using an etchant comprising about 1% by Volume of Sulfuric 23. The method of claim 22 wherein the etchant com
acid, about 4% by volume of phosphoric acid, and about 2% prises about 1% by volume of potassium hydroxide in water.
by Volume of Stabilized hydrogen peroxide. 24. An etchant for removing portions of a copper layer in
5. The method of claim 1 wherein the first layer is etched a Solar cell without Substantially etching a Solderable tin
using a Co-Bra Etch(R) etchant. layer, the etchant comprising hydrogen peroxide and Sulfuric
6. The method of claim 5 wherein the Co-Bra Etch(E) acid.
etchant is modified to comprise about 1% by volume of 25. The etchant of claim 24 wherein the etchant comprises
Sulfuric acid, about 4% by Volume of phosphoric acid, and about 1% by volume of Sulfuric acid, about 4% by volume
about 2% by volume of stabilized hydrogen peroxide. of phosphoric acid, and about 2% by volume of stabilized
7. The method of claim 1 wherein the first layer is etched hydrogen peroxide.
using a Perma-Etch etchant. 26. An etchant for removing portions of an aluminum
8. The method of claim 1 wherein the topmost metallic layer in a Solar cell without excessively etching a tin layer,
layer comprises tin and the first layer is etched using an the etchant comprising potassium hydroxide.
etchant comprising Sulfuric acid and hydrogen peroxide. 27. The etchant of claim 26 wherein the etchant comprises
9. The method of claim 1 further comprising: about 1% by volume of potassium hydroxide in water.
etching a Second layer comprising titanium-tungsten 28. A method of fabricating a solar cell, the method
using an etchant comprising hydrogen peroxide. comprising:
10. The method of claim 9 further comprising: etching a first layer comprising aluminum without Sub
etching a third layer comprising aluminum using an Stantially etching a topmost metallic layer of a Solar
etchant comprising potassium hydroxide. cell.
11. The method of claim 1 further comprising: 29. The method of claim 28 wherein the topmost metallic
layer comprises tin.
etching a Second layer comprising aluminum using an 30. The method of claim 28 wherein the first layer is
etchant comprising potassium hydroxide. etched using an etchant comprising potassium hydroxide.
12. The method of claim 11 wherein the etchant comprises 31. The method of claim 30 wherein the etchant com
about 1% by volume of potassium hydroxide in water. prises about 1% by volume of potassium hydroxide in water.
13. A method of etching a layer of material in a Solar cell, 32. The method of claim 28 wherein the first layer is
the method comprising: etched using an etchant that is Selective to an oxide layer
etching a copper layer Selective to a tin layer using an under the first layer.
etchant comprising Sulfuric acid and hydrogen perOX
ide.

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