SEMICONDUCTOR ETCHING METHODS
20210296187 · 2021-09-23
Inventors
Cpc classification
H01L21/465
ELECTRICITY
H01S5/18344
ELECTRICITY
H01L22/26
ELECTRICITY
H01S5/183
ELECTRICITY
H01L31/1828
ELECTRICITY
H01L33/0083
ELECTRICITY
H01L33/0062
ELECTRICITY
International classification
H01S5/20
ELECTRICITY
Abstract
A method of etching into a one or more epitaxial layers of respective semiconductor material(s) in a vertical cavity surface emitting laser (VCSEL) semiconductor structure, wherein the or each semiconductor material is a III-V semiconductor material, a III-N semiconductor material, or a II-VI semiconductor material is disclosed. The method comprises placing a substrate having the semiconductor structure thereon onto a support table in a plasma processing chamber, the semiconductor structure carrying a patterned mask on the surface of the semiconductor structure distal from the support table. The method also includes process steps of establishing a flow of an etch gas mixture through the plasma processing chamber and generating a plasma within the plasma processing chamber and simultaneously applying a radio frequency (RF) bias voltage to the support table; whereby the portion(s) of the semiconductor structure not covered by the patterned mask are exposed to the etch gas mixture plasma and are thereby etched to form at least one feature in the semiconductor structure; wherein more than 90% of the etch gas mixture consists of a mixture of silicon tetrachloride (SiCl.sub.4) and nitrogen (N.sub.2).
Claims
1-30. (canceled)
31. A method of etching into one or more epitaxial layers of respective semiconductor material(s) in a vertical cavity surface emitting laser (VCSEL) semiconductor structure, wherein the or each semiconductor material is a III-V semiconductor material, a III-N semiconductor material, or a II-VI semiconductor material, the method comprising: placing a substrate having the semiconductor structure thereon onto a support table in a plasma processing chamber, the semiconductor structure carrying a patterned mask on the surface of the semiconductor structure distal from the support table; and process steps of: establishing a flow of an etch gas mixture through the plasma processing chamber; and generating a plasma within the plasma processing chamber and simultaneously applying a radio frequency (RF) bias voltage to the support table; whereby the portion(s) of the semiconductor structure not covered by the patterned mask are exposed to the etch gas mixture plasma and are thereby etched to form at least one feature in the semiconductor structure; wherein more than 90% of the etch gas mixture consists of a mixture of silicon tetrachloride (SiCl.sub.4) and nitrogen (N.sub.2).
32. A method of etching into one or more epitaxial layers of respective semiconductor material(s) in a light-emitting diode (LED) semiconductor structure, wherein the or each semiconductor material is a III-V semiconductor material, a III-N semiconductor material, or a II-VI semiconductor material, the method comprising: placing a substrate having the semiconductor structure thereon onto a support table in a plasma processing chamber, the semiconductor structure carrying a patterned mask on the surface of the semiconductor structure distal from the support table; and process steps of: establishing a flow of an etch gas mixture through the plasma processing chamber; and generating a plasma within the plasma processing chamber and simultaneously applying a radio frequency (RF) bias voltage to the support table; whereby the portion(s) of the semiconductor structure not covered by the patterned mask are exposed to the etch gas mixture plasma and are thereby etched to form at least one feature in the semiconductor structure; wherein more than 90% of the etch gas mixture consists of a mixture of silicon tetrachloride (SiCl.sub.4) and nitrogen (N.sub.2).
33. A method of etching into one or more epitaxial layers of respective semiconductor material(s) in a photodiode semiconductor structure, wherein the or each semiconductor material is a III-V semiconductor material, a III-N semiconductor material, or a II-VI semiconductor material, the method comprising: placing a substrate having the semiconductor structure thereon onto a support table in a plasma processing chamber, the semiconductor structure carrying a patterned mask on the surface of the semiconductor structure distal from the support table; and process steps of: establishing a flow of an etch gas mixture through the plasma processing chamber; and generating a plasma within the plasma processing chamber and simultaneously applying a radio frequency (RF) bias voltage to the support table; whereby the portion(s) of the semiconductor structure not covered by the patterned mask are exposed to the etch gas mixture plasma and are thereby etched to form at least one feature in the semiconductor structure; wherein more than 90% of the etch gas mixture consists of a mixture of silicon tetrachloride (SiCl.sub.4) and nitrogen (N.sub.2).
34. A method according to claim 31, wherein at least 95% of the etch gas mixture consists of silicon tetrachloride (SiCl.sub.4) and nitrogen (N.sub.2), preferably substantially 100%.
35. A method according to claim 31, wherein the etch gas mixture further comprises one or more inert gases, such as helium, preferably forming less than 5% of the etch gas mixture.
36. A method according to claim 31, wherein the silicon tetrachloride (SiCl.sub.4) is the only halogen-bearing gas in the etch gas mixture present at more than trace levels.
37. A method according to claim 31, wherein the etch gas mixture does not contain more than a trace level of boron trichloride (BCl.sub.3), preferably no boron trichloride.
38. A method according to claim 31, wherein the ratio of silicon tetrachloride to nitrogen (SiCl.sub.4:N.sub.2) in the etch gas mixture is in the range of about 1:3 to 3:1, preferably in the range of about 1:2 to 4:3, most preferably about 1:2.
39. A method according to claim 31, wherein the or each semiconductor material is a binary, ternary or quaternary semiconductor material.
40. A method according to claim 31, wherein the or each semiconductor material is any of: GaN, GaAs, AlGaAs, InGaAs or AlInGaP.
41. A method according to claim 31, wherein the etch gas mixture has a total gas flow rate in the range 5 sccm to 200 sccm, preferably 80 to 120 sccm, more preferably around 100 sccm.
42. A method according to claim 31, further comprising controlling the pressure within the plasma processing chamber to a value in the range 0.5 to 10 mTorr.
43. A method according to claim 31, wherein the process steps are controlled such that the base of the etched feature(s) has a depth which varies across the width of the etched feature by no more than 200 nm, preferably by no more than 4%, more preferably no more than 3%, still preferably no more than 2% of the average feature depth.
44. A method according to claim 31, wherein the process steps are controlled such that the rate of etching is at least 500 nm/min.
45. A method according to claim 31, wherein the process steps are controlled such that the or each etched feature has a wall angle (α) between 60 and 80 degrees, preferably between 65 and 75 degrees.
46. A method according to claim 31, wherein the steps are controlled such that the semiconductor to mask etch selectivity is at least 4:1, the patterned mask preferably comprising silicon nitride.
47. A method according to claim 31, further comprising (i) halting the etching after a predetermined period of time has elapsed or (ii) monitoring the progress of the etching and preferably halting the etching when a predetermined depth has been reached and/or when a predetermined layer in the semiconductor structure has been reached, wherein preferably the progress of the etching is monitored using an optical interferometer or optical emission spectroscopy.
48. A method of processing a semiconductor structure, comprising performing the method of claim 31 as one of a sequence of processing steps, the other processing steps each comprising any of a deposition step, a passivation step, a heat-treatment step and another etching step, wherein preferably the sequence of processing steps is cyclical.
49. A method according to claim 48, wherein the sequence of processing steps defines an atomic layer etching process or a reactive ion etching process.
50. A semiconductor structure etched in accordance with the method of claim 31.
Description
[0047] Examples of etching methods and apparatus therefor in accordance with the present invention, will now be described and contrasted with conventional techniques with reference to the accompanying drawings, in which: —
[0048]
[0049]
[0050]
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[0055]
[0056]
[0057] The plasma processing tool 1 is equipped with a plasma source for generating a plasma within the process chamber by means of an electrical discharge. Here, the plasma source is depicted as an inductively-coupled plasma source comprising a coil 9 surrounding chamber 2, which is supplied with RF power from power supply 10 via a RF matching unit 11. The RF matching unit 11 is configured to match the plasma impedance to that of the RF supply 10 in order to maximise efficiency of power transfer from the supply to the plasma. An example of a suitable matching unit is disclosed in WO-A-2010/073006. Other types of plasma source such as a capacitively-coupled plasma (CCP) or a microwave plasma source could be used instead.
[0058] The substrate 30 is mounted in use on a platen 14. As described below, a bias voltage is applied in use to the substrate 30 and this is achieved by connecting a voltage source 12 to the platen 14. If an RF power supply 12 is used then an Automatic impedance Matching Unit (AMU) may preferably be provided to ensure good coupling of power from the power supply 12 to the wafer table 14. The tool 1 may further comprise a temperature control unit 16 such as a heater and/or cooling system for adjusting the processing temperature of the substrate (additional devices for heating and/or cooling of the process chamber and plasma source may be provided to assist with process control and/or to maintain hardware stability). For instance, where etching is primarily to be carried out, the substrate is preferably cooled using a circulating coolant to prevent the significant amount of energy transferred to the substrate during ion bombardment and/or during exothermic chemical reactions causing an undesirable increase in the substrate temperature.
[0059] The devices operate upon instruction from a controller 20, such as a programmable logic controller (PLC) or similar. In some cases, more than one controller can be provided, with each controller controlling one or a subset of the devices. The controller is also connected to a user interface device such as a computer workstation 25 for receiving input from the user and/or returning outputs.
[0060] In
[0061] An example of a semiconductor structure 30 to be etched is shown in schematic cross-section in
[0062] In the present example, the VCSEL semiconductor structure 30 is based on a support substrate 31 such as silicon, sapphire or the like followed by a metal contact layer 32. Alternatively the support substrate 31 can be a compound semiconductor wafer and the metal contact layer 32 is omitted. Next there is a substrate 33 such as n-GaAs, followed by a first reflector 34 such as a distributed Bragg reflector which in practice is formed of a plurality of sub-layers with alternating refractive index. For example, the sub-layers may be alternating layers of n-AlGaAs and n-GaAs. In
[0063] Detailed examples of the etch process itself will be provided below, but first
[0064]
[0065]
[0066] To perform the etch, the masked semiconductor structure 30 (such as that shown in
[0067] Typically, an etch gas mixture will contain one or more of the following components and the composition overall is optimised by experiment: [0068] 1. One or more gases which provide the feedstock for the targeted volatile reaction products, often a halogen-bearing gas or a methyl-forming mixture. [0069] 2. Optionally an inert gas, normally a noble gas with substantial mass to promote the effects of ion bombardment in disrupting bonds in the solid material. Argon is the usual gas for this purpose. [0070] 3. Optionally, a diluent gas with minimal impact on the process chemistry. This is usually a noble gas, and helium is often chosen for its lack of chemical interaction together with its low mass to avoid sputtering. [0071] 4. Optionally, a gas to steer the chemistry. Hydrogen or oxygen are the usual choices, being chemically active in the plasma. Additions up to 20% are known to optimise the production of certain radicals, or to promote or suppress the formation of polymers where these can be formed. [0072] 5. Optionally, a gas to promote sidewall passivation and prevent undercut. Boron trichloride and silicon tetrachloride are both potential candidates here and have been used in mixtures with each other, or with chlorine, for etching compound semiconductor materials.
[0073] To illustrate the benefits of the etch gas mixtures proposed for use in embodiments of the present invention, first, results obtained using etch gas mixtures according to comparative examples will be described for contrast.
[0074]
TABLE-US-00001 TABLE 1 Etch Footing BCl.sub.3 SiCl.sub.4 Cl.sub.2 N.sub.2 rate Selectivity height Sample (sccm) (sccm) (sccm) (sccm) (nm/min) ratio % 1 (FIG. 6) 10 0 10 10 612 2.8 7.8 2 0 10 10 10 744 3.2 7.8 3 (FIG. 7) 10 10 0 10 670 3.3 11.9
[0075] Further tests with increased amounts of boron trichloride (BCl.sub.3) led to increased footing heights and hence were found to be disadvantageous.
[0076] Tests were then carried out using etch gas mixtures of SiCl.sub.4 and N.sub.2 forming the vast majority of the total gas flow (over 90%), in accordance with embodiments of the present invention.
[0077] It was further found that increasing the process pressure can also help to increase the etch rate without worsening the footing height and this is illustrated in sample test 11, the results of which are shown in
TABLE-US-00002 TABLE 2 Plasma Process Etch SiCl.sub.4 N.sub.2 power pressure rate Selectivity Footing Sample (sccm) (sccm) (W) (mT) (nm/min) ratio % 4(FIG. 8) 10 20 350 1 349 2.4 3.9 5 10 0 350 1 466 2.7 11.8 (20Ar) 6 10 20 500 1 379 2.2 2.2 7 (FIG. 9) 10 20 750 1 412 1.8 2.2 8 20 30 750 1 555 2.1 2.5 9 20 20 1500 1 618 2.1 2.4 10 20 15 1500 1 754 2.4 3 11(FIG. 10) 12 20 900 6 800 4.8 0.7
[0078] It will be seen that all of the examples utilising etch gas mixture consisting predominantly of SiCl.sub.4 and N.sub.2 in varying proportion achieved a reduced footing height as compared with the other etch gas mixtures tested. Ratios of SiCl.sub.4 to N.sub.2 ranging from 1:2 to 4:3 were tested and found to give good results although, in general, mixtures having more N.sub.2 than SiCl.sub.4 were demonstrably better.
[0079] As noted above, SiCl.sub.4 and N.sub.2 should together make up over 90% of the etch gas mixture although as in the present examples other gases may be present to a minor extent, i.e. forming less than 10% of the mixture and preferably less than 5%. The helium background mentioned in the present examples falls within this category and is provided here to improve heat transfer between the wafer 30 and table 14.
[0080] In all of the samples 4, 5 and 7 to 12 discussed above, the angle α between the trench wall and the horizontal was found to be in the region of 60 to 80 degrees, typically around 75 degrees. The etch depth d in all cases was between 4 and 5 microns, on average around 4.669 microns.
[0081] Etch rates of over 500 nm per minute were achieved depending on the process parameters, and footings of less than 4% or preferably less than 3% were achieved. Masks selectivity ratios of up to 4.8 were also achieved. Overall it was noted that the etch resulted in smooth etch surfaces which were residue free.
[0082] The etching process can be brought to an end in various different ways. For example, the etch could be performed for a predetermined period of time after which duration has elapsed the process will be halted.
[0083] Alternatively, means may be provided for monitoring the progress of the etch such that it can be halted once a particular depth or layer within the structure 30 has been reached.
[0084] In
[0085] The etch process described may be a standalone etching procedure forming a complete process by itself, or could be a part of a longer overall process including multiple process steps or phases. For example, the overall process could be a cyclical etching and passivation process such as the Bosch process, and the described etch method could be used to implement the etching steps within that process.