Methods of metal assisted chemical etching iii-V semiconductors are provided. The methods can include providing an electrically conductive film pattern disposed on a semiconductor substrate comprising a iii-V semiconductor. At least a portion of the iii-V semiconductor immediately below the conductive film pattern may be selectively removed by immersing the electrically conductive film pattern and the semiconductor substrate into an etchant solution comprising an acid and an oxidizing agent having an oxidation potential less than an oxidation potential of hydrogen peroxide. Such methods can form high aspect ratio semiconductor nanostructures.
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0. 19. An electronic device comprising:
an array of nanopillars protruding from a base substrate, each nanopillar having a quantum well structure comprising a portion of the base substrate, a second layer on the base substrate and a first layer on the second layer,
wherein the first layer comprises a p-type or an n-type iii-V semiconductor, the second layer comprises a semi-insulating iii-V semiconductor, and the base substrate comprises a p-type or an n-type iii-V semiconductor opposite to that of the first layer.
1. A method of metal assisted chemical etching, the method comprising:
providing an electrically conductive film pattern disposed on a semiconductor substrate, the semiconductor substrate comprising a iii-V semiconductor; and
selectively removing at least a portion of the iii-V semiconductor immediately below the conductive film pattern by immersing the electrically conductive film pattern and the semiconductor substrate into an etchant solution comprising an acid and an oxidizing agent having an oxidation potential less than an oxidation potential of hydrogen peroxide.
15. A method of metal assisted chemical etching,
the method comprising:
providing a conductive film pattern disposed on a semiconductor substrate, the semiconductor substrate comprising a iii-V semiconductor; and
selectively removing at least a portion of the iii-V semiconductor immediately below the conductive film pattern by immersing the conductive film pattern and the semiconductor substrate into an etchant solution comprising an acid and an oxidizing agent selected from the group consisting of potassium permanganate (KMnO4) and potassium persulfate (K2S2O8).
2. The method of
7. The method ofclaim 1, wherein the acid is selected from the group consisting of sulfuric acid (H2SO4) and hydrofluoric acid (H F).
8. The method of
9. The method of
10. The method of
11. The method of
generating holes (h+) from the oxidizing agent on the conductive film pattern;
diffusing the holes (h+) to a boundary of the conductive film pattern, iii-V semiconductor, and etchant solution; and
removing the holes (h+) from semiconductor substrate substantially immediately upon the holes (h+) reaching the boundary.
12. The method of
13. The method of
14. The method of
17. The method of
18. The method of
0. 20. The electronic device of claim 19, wherein the iii-V semiconductor is selected from the group consisting of GaAs, InAs, GaP, InP, InGaAs and InGaP.
0. 21. The electronic device of claim 19, wherein the nanopillars have a width or diameter in a range from about 10 nm to about 1000 nm.
0. 22. The electronic device of claim 21, wherein the width or diameter is in the range from about 500 nm to about 1000 nm.
0. 23. The electronic device of claim 19, further comprising an electrically insulating material on the base substrate, the electrically insulating material surrounding each nanopillar and extending from the base substrate to a tip portion of the first layer.
0. 24. The electronic device of claim 23, further comprising an electrically conductive material on the tip portion of the first layer.
0. 25. The electronic device of claim 24, wherein the electrically conductive material comprises an electrically conductive transparent oxide, and wherein the electrically insulating material comprises an oxide or a polymer.
0. 26. The electronic device of claim 25, wherein the polymer comprises a photopolymer.
0. 27. The electronic device of claim 19, wherein the nanopillars comprise a length-to-width aspect ratio of at least about 5:1.
0. 28. The electronic device of claim 19, wherein the first layer comprises p-type GaAs, the second layer comprises intrinsic GaAs or intrinsic InGaAs, and the base substrate comprises n-type GaAs.
0. 29. The electronic device of claim 19 being selected from the group consisting of LED, solar cell and laser.
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The n-type GaAs samples described herein were initially prepared on a quarter of a purchased n-type GaAs wafer. These wafers were then cut into many smaller pieces to allow for multiple trials. The GaAs wafers used were (100) interface with a doping of Nd=2×1018 cm−3. Two different patterns were used for the GaAs MacEtch. The larger of the two patterns includes 0.3 mm×0.3 mm squares while the others are nanowire arrays of 1.0, 0.6, and 0.4 μm. The pattern, schematically illustrated in
The samples were individually subjected to a different etching solution that included deionized water (DI), H2SO4 or HF, and KMnO4 or K2S2O8. All of the square patterned samples were subjected to 30 mL HF and 15 mL DI for a duration of 3 minutes with varying concentrations of oxidizing agent. During etching, the acid and oxidizing agent concentrations were kept stable within a range that typically varied between 15 and 30 mL of acid with 0 to 15 mL of DI water. The hydrofluoric acid used was 49% by mass purchased from J. T. Baker. Since both of the oxidizing agents are solid reagents, they were mixed in the solution of HF:DI for five minutes prior to adding the GaAs sample. When both oxidizing agents were in the concentration at the same time, KMnO4 was always added first. All the GaAs samples were analyzed and measured using a Hitachi S4800 SEM.
Large Pattern Etching Examples
Larger square patterns on GaAs were used to compare the effect of an increasing concentration of oxidizing agent at a constant volume of HF and DI. The oxidizing agent was increased three different ways: (1) by increasing the amount of KMnO4 with no K2S2O8 present (
As observed in
Similarly, the horizontal side etch was observed to increase linearly with increasing KMnO4 when K2S2O8 was kept constant at 62 mM K2S2O8. As shown in
Increasing potassium persulfate resulted in a decrease in both vertical and side etching. At 103 mM K2S2O8 (
Similar surface defects occur in the other two examples as well. While none of them formed vacancies beneath the surface, there were similar surface morphologies evident only near the GaAs gold interface. Both
Nanowire Formation Examples
While silicon has already been able to form nanowires by metal assisted chemical etching with much success, it has yet to be proven for III-V materials. Using the perforated patterns mentioned above (such as in regard to
With a solution of only KMnO4 and HF, nanowires of different morphologies were observed at distinct KMnO4:HF concentrations (
Also, these examples were done in a 30 mL Pyrex container with a 32 mm diameter. The HF reacted with the SiO2 and B2O3 to dilute the solution. However, the examples done in the Pyrex glass were more consistent than those done in the plastic container.
As observed in
However, some wires obtained were fairly smooth as observed in
Nanostructures were observed using other solutions as well.
A small chuck of gold was placed in the solution during the K2S2O8 and KMnO4 etch. By producing an additional surface for oxidation to occur, the small chunk of gold essentially reduced the effect of the oxidizing agent. Without the piece of gold, the side etch was too extensive and only miniature spikes were etched out of the GaAs substrate.
Even better nanowires were formed with sulfuric acid and potassium permanganate, as shown
By adapting metal-assisted chemical etching methods to GaAs, nanoscale structures can be successfully etched into substrates. Similar methods can be used to etch through other heterostructure III-V material. By exploiting the effect different acids and oxidizing agents have on the etching process, different nanostructures can be formed for a variety of applications, including nanowires of multiple morphologies, with zigzag shapes and along angled interfaces.
Regardless of the type of the semiconductor, an ideal MacEtch solution is substantially inert without the presence of metal. Although H2O2 has been proven to be a suitable MacEtch agent for silicon, it has been shown to etch (100) GaAs in either acidic or base solution without the presence of metal catalyst. MacEtch of III-V material can be performed by using appropriate etching conditions resulting in the highest differential etch rate for the III-V semiconductors, where differential etch rate refers to the difference in the etch rate with and without metal present. Oxidizing agents with weaker oxidation potentials (e.g., KMnO4) can be used to prevent nonmetal-catalyzed etching, while maintaining a reasonable etch rate in the presence of metal.
Described below is additional discussion of how the parameters of the MacEtch process can be selected for different III-V materials. Also described are additional etching characteristics of n-type GaAs wafers patterned by gold using soft lithography and etched with KMnO4 as the oxidizing agent in acidic (H2SO4 or HF) solutions. Of interest is the influence of solution concentration and temperature on the etching characteristics.
As described above and further below ordered arrays of high aspect ratio GaAs nanostructures have been formed using Au-MacEtch. In the below additional MacEtch examples, Epi-ready Si-doped (100) GaAs substrates acquired from AXT, Inc. with a doping concentration of 1×1018 to 4×1018 cm3 were used for MacEtch. Potassium permanganate (KMnO4), an oxidizing agent that has an oxidation potential lower than that of H2O2 (see Table I), was mixed with deionized water (DI) and either sulfuric acid (H2SO4) or hydrofluoric acid (HF). The overall etching of GaAs using KMnO4 can be described by the following chemical reaction: GaAs+MnO−+H+→Ga3++Asn++Mn2++H2O, with n equal to 3 or 5. In MacEtch, the metal catalyst acts as the cathode and the semiconductor acts as the anode. Table I lists relevant half reactions involving chemical species used for etching, as well as possible products and participating reactants in the overall reaction. Several possible products of the etching reaction with mass and charge balanced are listed in Table II. The etching was carried out at either room temperature or at 30 to 45′ C. for a period of 3 to 5 min, as indicated below. No stirring was done during etching.
TABLE H
Half-cell electrochemical potentials.
E°/V
Anode Reaction
Gallium
Ga → Ga3+ + 3e
0.549
Ga → Ga+ + e−
0.2
Ga + H2O → GaOH2+ + H+ + 3e−
0.498
Ga + 4OH− → H2GaO3− + H2O + 3e−
1.219
Arsenic
As + 3H+ + 3e− → AsH3
−0.608
2As + 3H2O → As2O3 + 6H+ + 6e−
−0.234
As + 2H2O → HAsO2 + 3H′ + 3e
−0.248
HAsO2 + 2H2O → H3AsO4 + 2H+ + 2e−
−0.560
As + 4OH− → AsO2− + 2H2O + 3e−
0.68
AsO2− + 4OH− → AsO43− + 2H2O + 2e−
0.71
Silicon
Si + 6F− → SiF62− + 4e−
1.24
Si +H2O → SiO + 2H+ + 2e−
0.8
Si + 2H2O → SiO2 (quartz) + 4H+ + 4e−
−0.857
Si + 6OH− → SiO32− + 3H2O + 4e−
1.697
Cathode Reaction
MnO4− + 8H+ + 5e− → Mn2+ + 4H2O
1.507
MnO4− + 4H− + 3e− → MnO2 + 2H2O
1.679
H2O2 + 2H+ + 2e− → 2H2O
1.776
S2O82− + 2H′ + 2e− → 2HSO4−
2.123
Gold
Au+ + e− → Au
1.692
Au3+ + 2e− → Au+
1.401
Au3+ + 3e− → Au
1.498
Au2+ + e− → Au+
1.8
Overall Reaction
GaAs + MnO4− + H+ → Ga3+ + As3+ + Mn2+ + H2O
Overall reaction with possible forms of the products (balanced)
GaAs + 2KMnO4 + H2O + 5HF → HAsO2 + GaF3•3H2O +
2MnO2 + 2KF
3GaAs + 8KMnO4 + 17HF + 5H2O → 3H3AsO4 + 3(GaF3•3H2O) +
8MnO2 + 8KF
10HaAs + 12KMnO4 + 33H2SO4 → 10HAsO2 + 12MnSO4 +
6K2SO4 + 5Ga2(SO4)3 + 28H2O
10HaAs + 16KMnO4 + 39H2SO4 → 10H3AsO4 + 16MnSO4 +
K2SO4 + 5Ga2(SO4)3 + 24H2O
Nanoscale gold mesh patterns, with hole size ranging between 500 and 1000 nm, were prepared using a soft lithography method. First, a layer of SiNx was deposited on top of the GaAs, followed by a spin-coated layer of SU8 resist. Using a poly-(methyl methacrylate) (PMMA) stamp, the pattern was imprinted onto the SU8. Next the depressed SU8 was removed using an oxygen plasma etch. The sample was then subject to a CHF4 etch to remove the exposed SiNx. Following this step, a 20 nm layer of Au was evaporated on the GaAs surface. Native oxide on GaAs was removed using (HCL: DI=1:1) solution just before evaporating Au. The remaining SiNx and SU8 were removed with sonication in a diluted HF solution. Also tested were micrometer square patterns of 300×300 μm2 separated by 125 μm wide strips of gold formed with standard optical lithography using AZ5214 photoresist. SEM images were obtained using a Hitachi 4800 microscope and photoluminescence (PL) spectra were measured using a Renishaw micro-PL system with a 633 nm pump laser and a CCD detector at room temperature.
As mentioned above, MacEtch begins when holes (h+) are generated from the oxidant on the metal surface and then diffuse to the semiconductor. The holes (h+) can then subsequently be consumed by oxidizing the semiconductor directly underneath the metal to form soluble product in the acidic solution. This leads to vertical etching. Alternatively, the holes can diffuse outside of the metal-semiconductor interface to areas around the metal to induce lateral etching. The aspect ratio of a produced structure is inherently related to the proportion of vertical to lateral etching, which is the essence of the MacEtch mechanism. Processing factors that affect the dynamics of MacEtch can be classified into three categories. (1) semiconductor type and doping; (2) metal type, feature size, and density; and (3) solution components, concentration, temperature, and local concentration fluctuation. The examples herein focused on parameters of the third factor that limits aspect ratios, e.g., the solution. In particular, the effect was explored of oxidizing agent potential and concentration, chemical end product, accessibility to solution as a result of metal pattern size, and temperature on the etching dynamics and aspect ratio of GaAs nanostructures produced by this method.
In order to produce high aspect ratio structures, lateral etching should be suppressed.
Note that patterns of hundreds of micrometers were used to evaluate side etch. If the side etch is larger than the radius of the nanostructure's lateral dimension, the etching will result in polishing with no discernible structure formation. Due to the difference in the supply of holes (h+) for oxidation and end product removal rate, the selection of the parameters of etching recipe varies as a function of metal pattern size and connectivity. MacEtch of GaAs at nanoscale dimensions was found to be sensitive to all etching parameters. For gold mesh patterns at submicrometer scales, most combinations of oxidant to acid ratio, dilution, and temperature resulted in either no etching or polishing from overetching. A suitable etching condition is determined by calibrating between the two extremes.
Without being bound by theory, it is hypothesized that at this temperature, the etching reaction is dissolution limited. The rate-determining step is the removal of the oxidized Ga3+ and Asn+ (n=3+ or 5+) into solution (e.g., Ga2(SO4)3 and HAsO2). As a result, the holes (h+) generated at the gold surface are not consumed in time and instead diffuse laterally to promote etching of the bare GaAs. Similar reverse MacEtch was reported for InP under photoirradiation. In that case, the above bandgap photons generate electrons and holes in the bare InP area; the electrons then diffuse and recombine with the holes generated from metal-catalyzed oxidant reduction in the metal-covered area causing holes to accumulate and etch the bare InP region. These results indicate that etching temperature can affect the dynamics of carrier diffusion, oxidation, and product removal, all of which effect the spatial profile of GaAs structures generated by patterned MacEtch.
Furthermore, striking zigzagging high aspect ratio nanowires are formed by MacEtch using a solution of KMnO4 and HF in a glass beaker at room temperature. Shown in
It has been reported that zigzag silicon nanowires were formed using (111) Si wafers through MacEtch with solution-based gold catalyst AgNO3 (Chen, H.; Wang, H.; Zhang, X.-H.; Lee, C.-S.; Lee, S.-T. Nano Lett. 2010, 10, 864-868). Notably, an intentionally scratched rough surface led to zigzag, while polished smooth surface yielded straight wires. In another report (Kim, J.; Kim, Y. H.; Choi, S.-H.; Lee, W. ACS Nano 2011, 5, 5242-5248), an initial porous silicon layer was deemed important for the formation of zigzag Si nanowires for Si(100) surface using patterned gold mesh as catalyst at an elevated temperature (60° C.). The porous layer acted as a barrier to deter diffusion of MacEtch reactants in the unstirred solution, creating high and low concentrations as reactants were consumed because there was a delay in replenishing them. The zigzag morphology was also believed to be attributed to the concentration variations.
For GaAs, intentional surface roughening did not produce zigzagging structures. However, carrying out the reaction in a glass container with HF acid produced the zigzag morphology while other container materials did not, implying that the borosilicate glass container participated in the etching reaction. Without being bound by theory, it is hypothesized that the glass surrounding the solution is constantly turning HF into H2O, which creates a concentration gradient that drives the diffusion of HF directly above the semiconductor wafer piece toward the container walls. In competition with the outward diffusion, HF is consumed from reacting with GaAs during MacEtch, causing the diffusion to shift back toward the wafer piece to rebalance the concentration. The constant modulation of flux during etching creates a periodic concentration variation similar to the zigzagging silicon nanowire etching condition reported by Kim et al. Although the borosilicate container reaction replicated an extreme case of concentration variations during etching, the resulting nanowire morphology clearly demonstrates the susceptibility of GaAs MacEtch to local solution fluctuations.
By adapting the etching solution to GaAs, the MacEtch process, a wet but directional etching method, has been demonstrated to produce high aspect ratio semiconductor nanoscale structures beyond just silicon. In contrast to MacEtch of silicon, the process window for GaAs is more sensitive to the rate of oxidation with and without the gold catalyst and rate of dissolution for etching product removal, as well as to changes in the local concentration during etching. By exploiting the effect of etching parameters, different nanostructures can be formed for a variety of applications, including DBR or DFB lasers, photonic crystals, LEDs with periodic roughening surfaces, and solar cells with light trapping nanostructures. Since the etching takes place at a temperature near room temperature, no metal contaminants should be incorporated in the core of the nanopillars, and surface contamination can be removed. Because there is no high energy ions involved, as in the case of dry etching, surface damage should not be a concern. Because the aspect ratio is essentially limited by etching time, as long as unassisted etching mechanism such as side etching can be suppressed, extremely high aspect ratio vertical structures can be generated. Although only n-type GaAs is demonstrated here, using teachings disclosed herein, etching parameters can be selected for MacEtch to work for other III-V materials of various doping types and levels as well as heterostructures. The realization of high aspect ratio III-V nanostructure arrays by MacEtch can potentially transform the fabrication of a variety of optoelectronic device structures including DBR and DFB semiconductor lasers, where surface grating is currently fabricated by dry etching. It also brings affordability and possibly new device concepts for III-V nanostructure based photonic devices.
n-GaAs, SI-GaAs, p-GaAs Compositions and Devices
MacEtch was performed on GaAs (100) substrates with three different doping types: semi-insulating (SI), Si-doped (n=˜1−3×1018 cm−3), and Zn-doped (p−1×1018 cm−3). After native oxide removal in a dilute HCl solution, a 35 Å Au-layer was deposited on the GaAs substrates via electron-beam evaporation, followed by soft-lithography patterning of gold to pattern various devices. MacEtch was performed in a solution including deionized water (DI), 49% hydrofluoric acid (HF) as the etching agent, and potassium permanganate (KMnO4) as the oxidizing agent. Scanning electron microscopy (SEM) was performed using a Hitachi S-4800 microscope and photoluminescence (PL) spectra were obtained through the use of a Renishaw in Via μ-PL system at room temperature with excitation provided by laser emission centered at 633 nm.
TABLE III
Molar Concentrations and Concentration Ratios
[HF]
[KMnO4]
[HF]/[KMnO4]
[KMnO4]/[HF]
(a)
0.14M
7.9E−6M
17722
5.6E−5
(b)
0.28M
6.35E−6M
44094
2.3E−5
(c)
0.56M
3.17E−6M
176654
5.6E−6
(d)
0.7M
1.59E−6M
440257
2.2E−4
Samples of p-GaAs were also etched.
Samples of p-i-n GaAs were also tested. The p-i-n GaAs samples were produced by forming an intrinsic or non-doped GaAs (i-GaAs) layer on an n-type GaAs (n+ GaAs) substrate. A p-type GaAs (p-GaAs) layer was formed on the n+ GaAs substrate such that the i-GaAs layer was sandwiched between the n+ GaAs substrate and the p-GaAs layer. The i-GaAs layer was about 300 nm thick and the p-GaAs layer was doped with Zn and was about 300 nm thick. All of the p-i-n GaAs samples were produced using a gold pattern.
A first sample of p-i-n GaAs was etched in a solution of 10 mL HF, 20 mL DI, 0.1 g of KMnO4 at room temperature for 30 minutes.
The first sample of p-i-n GaAs was then etched in a solution that was the same for an additional 15 minutes.
A second sample of p-i-n GaAs was etched in a solution the same as the first sample for 10 minutes to see the early etch stages where lateral etching started.
The second sample was then further etched in a solution of solution of 20 mL HF, 10 mL DI, 0.1 g of KMnO4 at room temperature for 3.5 minutes.
The morphology of GaAs pillars may also be altered as a function of the MacEtch solution employed. While vertical etch rates are quenched under higher dilution levels, lateral etch rates may be enhanced. This allows for a variation of the nanostructure geometry. Shown in
MacEtch can be used to form p-i-n GaAs or InGaAs/GaAs quantum well nanopillar arrays for use in LED and solar cell applications.
In order to produce an LED, a sample similar to that of the p-i-n GaAs of
Superlattice heterostructured samples including six periods of alternating layers of GaAs and InxGa1-xAs (x=0.5) were grown via metalorganic chemical vapor depositions (MOCVD).
The etching methods described herein offer the potential to create high quality III-V photonic devices quickly and efficiently. For example, the realization of high aspect ratio III-V nanostructure arrays by wet etching can potentially transform the fabrication of a variety of optoelectronic device structures including distributed Bragg reflector (DBR) and distributed feedback (DFB) semiconductor lasers, where the surface grating is currently fabricated by dry etching. Because it can occur at room temperature, MacEtch is not likely to introduce metal contamination, in contrast to bottom-up high-temperature metal-catalyzed nanowire growth techniques, and since MacEtch is a wet etch process, MacEtch avoids ion-induced surface damage typically seen in dry etch processes. This can be crucial to III-V nanostructures for optoelectronic applications. For silicon, such surface damage can be repaired by thermal annealing. However, for compound semiconductors, such as GaAs, thermal repair is not completely effective mainly because of the difficulty of maintaining stoichiometry.
Such III-V nanostructures can be also used in other devices such as distributed feedback (DFB) and distributed Bragg reflector (DBR) lasers, photonic crystals, solar cells and light emitting diodes (LEDs) that involve surface relief structures for light trapping, and simply creating micron and nanometer scale mesa structures that is currently done by dry etching. Since MacEtch is a wet etch, the container holding the solution can be sized to fit essentially any desired device.
Although the present invention has been described in considerable detail with reference to certain embodiments thereof, other embodiments are possible without departing from the present invention. The spirit and scope of the appended claims should not be limited, therefore, to the description of the preferred embodiments contained herein. All embodiments that come within the meaning of the claims, either literally or by equivalence, are intended to be embraced therein.
Furthermore, the advantages described above are not necessarily the only advantages of the invention, and it is not necessarily expected that all of the described advantages will be achieved with every embodiment of the invention.
Li, Xiuling, Chern, Winston, Shin, Jae Cheol, Dejarld, Matthew T., Mohseni, Parsian Katal
Patent | Priority | Assignee | Title |
Patent | Priority | Assignee | Title |
6790785, | Sep 15 2000 | Board of Trustees of the University of Illinois, The | Metal-assisted chemical etch porous silicon formation method |
8334216, | Mar 02 2010 | NATIONAL TAIWAN UNIVERSITY | Method for producing silicon nanostructures |
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