US20050042876A1 - Method of etching and etching apparatus - Google Patents

Method of etching and etching apparatus Download PDF

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Publication number
US20050042876A1
US20050042876A1 US10/938,789 US93878904A US2005042876A1 US 20050042876 A1 US20050042876 A1 US 20050042876A1 US 93878904 A US93878904 A US 93878904A US 2005042876 A1 US2005042876 A1 US 2005042876A1
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gas
flow rate
etching
equal
oxide film
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Noriyuki Kobayashi
Kenji Adachi
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Tokyo Electron Ltd
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Tokyo Electron Ltd
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Assigned to TOKYO ELECTRON LIMITED reassignment TOKYO ELECTRON LIMITED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ADACHI, KENJI, KOBAYASHI, NORIYUKI
Publication of US20050042876A1 publication Critical patent/US20050042876A1/en
Priority to US11/780,797 priority Critical patent/US7943524B2/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76897—Formation of self-aligned vias or contact plugs, i.e. involving a lithographically uncritical step
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/311—Etching the insulating layers by chemical or physical means
    • H01L21/31105—Etching inorganic layers
    • H01L21/31111—Etching inorganic layers by chemical means
    • H01L21/31116—Etching inorganic layers by chemical means by dry-etching

Definitions

  • the present invention relates to an etching method and an etching apparatus, employed to a manufacturing process of a semiconductor device.
  • a self-alignment contact technology may be applied.
  • the contact hole 20 is formed in a self-aligning manner in a small and compact area between gates 12 while a protective film layer 14 such as a silicon nitride (SiN) film is formed on each gate 12 , thereby preventing the gate 12 from being etched in the course of forming the contact hole 20 .
  • a CF-based gas such as C 4 F 8
  • a gaseous mixture including O 2 is used as an etching gas for removing deposits.
  • the plasma etching employing the conventional processing gases as described above is disadvantageous in that as the aspect ratio of the contact hole becomes higher, because of the narrow gaps between the gates, the etching time becomes longer to prevent degradation of the capability to pierce an etching target and occurrence of an etching stop.
  • a large portion of a shoulder (edge) 14 a of the silicon nitride film, acting as a protective film layer formed on a surface of the gate 12 is extended into an inner space of the contact hole 20 to be formed through the silicon oxide film acting as the insulating film layer 16 . Therefore, the shoulder 14 a may be very readily etched.
  • the shoulder (edge) 14 a of the protective film layer 14 may be severely etched depending on etching selectivity of the insulating film layer 16 over the protective film layer 14 of the gate 12 , thereby rendering the gate 12 undesirably exposed thereto.
  • an object of the present invention is to provide a novel and improved etching method and etching apparatus thereof assuring an excellent controllability, in which etching selectivity of a silicon oxide film layer against a silicon nitride film layer of a gate can be increased.
  • the silicon nitride film layer, acting as a protective film layer of the gate can be strongly prevented from being etched while it becomes possible to form a contact hole with a high aspect ratio possible.
  • an etching method in which a processing gas is fed into an airtight processing chamber to generate a plasma therein and a silicon-containing oxide film formed on an object to be processed disposed in the processing chamber is selectively etched against a silicon nitride film, wherein the processing gas is a gaseous mixture including at least a fluorocarbon-based gas, a first deposit removing gas and a second deposit removing gas having a weaker deposit removing capability than the first deposit removing gas.
  • an etching apparatus in which a processing gas is fed into an airtight processing chamber to generate a plasma therein and a silicon-containing oxide film formed on an object to be processed disposed in the processing chamber is selectively etched against a silicon nitride film, wherein the processing gas is a gaseous mixture including at least a fluorocarbon-based gas, a first deposit removing gas and a second deposit removing gas having a weaker deposit removing capability than the first deposit removing gas.
  • an etching selectivity of the silicon-containing oxide film over the silicon nitride film is preferably set to a predetermined value by a ratio of a total flow rate of the first and the second deposit removing gases to a flow rate of the fluorocarbon-based gas, and a ratio of a flow rate of the second deposit removing gas to the flow rate of the fluorocarbon-based gas.
  • the silicon-containing oxide film is preferably a silicon oxide film
  • the fluorocarbon-based gas is C 4 F 6 gas
  • the first deposit removing gas is oxygen gas
  • the second deposit removing gas is nitrogen gas preferably.
  • the processing gas preferably includes an inert gas.
  • a ratio of a flow rate of the N 2 gas to a flow rate of the C 4 F 6 gas is preferably greater than or equal to about 25/8 and less than or equal to about 85/8, and a ratio of a total flow rate of the O 2 gas and the N 2 gas to the flow rate of the C 4 F 6 gas is preferably greater than or equal to about 15/4 and less than or equal to about 45/4.
  • the ratio of the flow rate of the N 2 gas to the flow rate of the C 4 F 6 gas is preferably greater than or equal to about 25/8 and less than or equal to about 85/8, and a ratio of the flow rate of the N 2 gas to the flow rate of the O 2 gas is preferably greater than or equal to about 5 and less than or equal to about 17.
  • an upper and a lower electrodes are installed opposite to face each other in the processing chamber, a first high frequency power is applied to the upper electrode, a frequency of a second high frequency power is applied to the lower electrode, a frequency of the second high frequency power being lower than that of the first high frequency power.
  • the frequency of the first high frequency power is about 60 MHz and that of the second high frequency power is about 2 MHz, preferably.
  • the silicon nitride film exists under the silicon oxide film, and the silicon oxide film is etched in a self-alignment contact process.
  • the present invention satisfies recent demands for improved integration of a semiconductor device and miniaturization of various elements formed on a semiconductor substrate.
  • 1 mTorr is equivalent to (10 ⁇ 3 ⁇ 101325/760) Pa and 1 sccm is equivalent to (10 ⁇ 6 /60) m 3 /sec.
  • FIG. 1 schematically illustrates an etching apparatus, to which an etching method in accordance with the present invention may be applied;
  • FIGS. 2 a and 2 b are sectional views of an objective substrate illustrating the etching of the objective substrate in accordance with the present invention
  • FIG. 3 is a graph showing the results of the etching of a silicon oxide film layer in accordance with the present invention.
  • FIG. 4 is a sectional view of an objective substrate illustrating the etching of the objective substrate in accordance with a conventional etching method.
  • FIG. 1 schematically illustrates a parallel plate type plasma etching apparatus, which is an embodiment of the etching apparatus in accordance with the present invention.
  • the plasma etching apparatus 100 includes a processing chamber 104 defined by a securely grounded processing vessel 102 , and a vertically movable lower electrode 106 included in a suscepter is installed in the processing chamber 104 .
  • An electrostatic chuck 110 connected to a high voltage DC power supply 108 is provided at an upper part of the lower electrode 106 and an object to be processed, for example a semiconductor wafer (hereinafter, referred to as “wafer”) W, is loaded on the electrostatic chuck 106 .
  • an insulating focus ring 112 is installed around the wafer W loaded on the lower electrode 106 .
  • the lower electrode 106 is connected to a second high frequency power supply 120 via a matching unit 118 .
  • an upper electrode 122 having a plurality of gas discharge openings 122 a is provided at a top of the processing chamber 104 , the top thereof facing against the lower electrode 106 .
  • An insulator 123 is interposed between the upper electrode 122 and the processing vessel 102 to electrically isolate the upper electrode 122 from the processing vessel 102 .
  • the upper electrode 122 is connected via a matching unit 119 to a first high frequency power supply 121 generating high frequency power to produce a plasma.
  • a second high frequency power is applied from the second high frequency power supply 120 to the lower electrode 106 , a frequency of the second high frequency power being lower than that of the first high frequency power generated from the first high frequency power supply 121 .
  • the frequency of the second high frequency power ranges from about 2 to about 13.56 MHz, and is preferably about 2 MHz.
  • a gas supply line 124 communicates with the gas discharge openings 122 a , wherein the gas supply line 124 is connected to a processing gas supplying system 126 a for supplying, for example, C 4 F 6 , a processing gas supplying system 126 b for supplying, for example, Ar, a processing gas supplying system 126 c for supplying, for example, N 2 , and a processing gas supplying system 126 d for supplying, for example, O 2 .
  • a processing gas supplying system 126 a for supplying, for example, C 4 F 6
  • a processing gas supplying system 126 b for supplying, for example, Ar
  • a processing gas supplying system 126 c for supplying, for example, N 2
  • a processing gas supplying system 126 d for supplying, for example, O 2 .
  • Each of the processing gas supplying systems 126 a , 126 b , 126 c and 126 d includes each of opening/closing valves 132 a , 132 b , 132 c and 132 d , respectively; includes each of flow rate controlling valves 134 a , 134 b , 134 c and 134 d , respectively; and are connected to a C 4 F 6 gas supply source 136 a , an Ar gas supply source 136 b , a N 2 gas supply source 136 c and an O 2 gas supply source 136 d , respectively.
  • a gas exhaust line 150 communicating with a vacuum exhaust unit is formed at a lower part of the processing vessel 102 and an inner space of the processing chamber 104 is maintained under reduced pressure by the vacuum exhaust unit.
  • FIG. 2A there is illustrated an example of layered structure of films, which will be etched in accordance with the present invention.
  • the layered structure of films is formed in accordance with the following procedure.
  • a gate 202 is formed on a silicon (Si) substrate 200 as a semiconductor substrate
  • a silicon nitride film layer 204 as a protective film layer is formed thereon in such a way that the gate 202 is coated over therewith.
  • a silicon oxide film layer 206 which includes SiO 2 and the like and acts as an insulating film layer, is formed on an entire surface of the resulting substrate by, for example, a chemical vapor deposition (CVD) process.
  • a photoresist film is applied on the silicon oxide film layer 206 and then patterned to form a contact hole 210 therethrough, thereby forming the photoresist layer 208 .
  • a processing gas which includes a C 4 F 6 gas as a fluorocarbon-based gas, an O 2 (oxygen) gas as a first deposit removing gas, a N 2 (nitrogen) gas as a second deposit removing gas and a gaseous mixture containing Ar, is introduced into the processing chamber 104 to conduct a plasma process, thereby performing the etching.
  • the C 4 F 6 gas is used as an etching gas
  • the Ar-containing gas is used as a dilution gas.
  • the O 2 and the N 2 gas are used to remove deposits generated by the etching.
  • N 2 gas is included as the gas for removing the deposits in addition to O 2 gas is because it is much easier to achieve a fine tuning in control over removing the deposits by controlling the flow rate of N 2 than controlling that of O 2 , since N 2 is much less powerful in removing the deposits than O 2 .
  • an amount of the deposits removed is increased as a flow rate of the deposit removing gas such as N 2 or O 2 , increases. In such a case, O 2 and N 2 have different deposit removing rates from each other.
  • an increase rate of the removed amount of deposit to an increase of its flow rate is a level of about ⁇ fraction (1/10) ⁇ - ⁇ fraction (1/20) ⁇ of that of O 2 .
  • a small increase in the flow rate of O 2 causes a big increase in the amount of the deposits removed, resulting in an excessive removal of the deposits.
  • N 2 which removes a relatively small amount of the deposit for an increase in its flow rate, is contained in the processing gas to readily control the amount of the removed deposit.
  • the processing gas does not contain O 2 but N 2 , and then since the N 2 gas has relatively poor deposit removing capability, the deposit is insufficiently removed, thereby rendering an etching stop occurring. Therefore, in the present invention, O 2 as well as N 2 is included in the processing gas.
  • N 2 has some deposit removing capability even though it is relatively poor, the etching selectivity of the silicon oxide film layer 206 over the silicon nitride film layer 204 cannot be made high, when its flow rate is excessively high. Therefore, it is necessary to properly control respective flow rates of gases, including N 2 .
  • a flow rate ratio of C 4 F 6 /Ar/O 2 (a flow rate of C 4 F 6 /a flow rate of Ar/a flow rate of O 2 ) was 16 sccm/800 sccm/10 sccm, temperatures of the lower and the upper electrodes in the processing chamber 104 were 40° C. and 60° C., respectively and a temperature of a sidewall of the processing chamber 104 was 50° C.
  • Pressures of a cooling gas as a back pressure gas (He gas) applied to the center and edges of a backside of the wafer were 5 Torr and 10 Torr, respectively.
  • the etching could be conducted under a 100% over-etching condition by only controlling the flow rate of N 2 .
  • the 100% over-etching condition means that the etching was performed for a time required to remove a layer that was twice as thick as the silicon oxide film layer 206 .
  • removal amounts t's of the shoulder (edge) 204 a of the silicon nitride film layers 204 were 112 nm, 118 nm and 134 nm, respectively, while selectivities of the silicon oxide film layer 206 over the shoulder (edge) 204 a of the silicon nitride film layers 204 [an etching rate of the silicon oxide film layer/an etching rate of the shoulder part (edge part) of the silicon nitride film layer] were 17.4, 15.9 and 12.6, respectively.
  • selectivities of the silicon oxide film layer 206 over the shoulder parts (edge part) of the photoresist layer 208 were 4.6, 5.2 and 5.0, respectively.
  • the removed amount of the shoulder (edge) 204 a of the silicon nitride film layer 204 was represented by a distance t between two straight lines which were inclined by an angle of 45 degrees with respect to the silicon substrate 200 and were drawn at the shoulder 204 a before and after, respectively, the silicon nitride film layer 204 was etched as shown in FIG. 2B .
  • a removed amount of a shoulder part (edge part) of the photoresist layer 208 was represented by a distance u between an upper surface of the photoresist layer 208 before the photoresist layer 208 was etched and a point, at which an etched portion of the photoresist layer 208 met a wall of the contact hole after the photoresist layer 208 was etched as shown in FIG. 2B .
  • the removal amounts t's of the shoulder (edge) 204 a of the silicon nitride film layers 204 were 84 nm, 73 nm and 84 nm, respectively, while the selectivities of the silicon oxide film layer 206 over the shoulder (edge) 204 a of the silicon nitride film layers 204 [an etching rate of the silicon oxide film layer/an etching rate of the shoulder part (edge part) of the silicon nitride film layer] were 23.1, 26.0 and 20.5, respectively.
  • the selectivities of the silicon oxide film layer 206 over the shoulder parts (edge part) of the photoresist layer 208 were 5.2, 7.8 and 7.8, respectively.
  • the flow rate of N 2 was 100 sccm
  • the flow rate ratio of C 4 F 6 /Ar/N 2 /O 2 (the flow rate of C 4 F 6 /the flow rate of Ar/the flow rate of N 2 /the flow rate of O 2 ) was 16 sccm/800 sccm/100 sccm/10 sccm
  • the etching rates of the silicon oxide film layer at the center portion, at the intermediate portion between the end portion and the center portion and at the end portion of the wafer W were 539.3 nm/min, 524.0 nm/min, and 500.0 nm/min, respectively.
  • the removed amounts t's of the shoulder (edge) 204 a of the silicon nitride film layers 204 were 47 nm, 51 nm and 65 nm, respectively, while the selectivities of the silicon oxide film layer 206 over the shoulder (edge) 204 a of the silicon nitride film layers 204 [an etching rate of the silicon oxide film layer/an etching rate of the shoulder part (edge part) of the silicon nitride film layer] were 41.3, 36.4 and 26.6, respectively.
  • the selectivities of the silicon oxide film layer 206 over the shoulder parts (edge part) of the photoresist layer 208 were 6.6, 6.8 and 10.0, respectively.
  • a horizontal axis represents the flow rate of the N 2 gas and vertical axes correspond to the etching rate and selectivity of the silicon oxide film layer, respectively. Further, averages of the values at the center portion, at the intermediate portion between the end portion and the center portion, and at the end portion of the wafer W are taken and plotted in FIG. 3 .
  • a line y 1 is a graph showing an interrelation between the flow rate of N 2 and the etching rate of the silicon oxide film layer
  • a line y 2 is a graph showing an interrelation between the flow rate of N 2 and the selectivity of the silicon oxide film layer over the shoulder part of the photoresist layer
  • a line y 3 is a graph showing an interrelation between the flow rate of N 2 and the selectivity of the silicon oxide film layer over the shoulder part of the silicon nitride film layer.
  • the desirable flow rate of N 2 is preferably within a range at which the selectivity of the silicon oxide film layer over the silicon nitride film layer is greater than or equal to about 20.0, and more preferably, within a range at which the selectivity of the silicon oxide film layer over the silicon nitride film layer is greater than or equal to about 30.0, practically.
  • the flow rate of N 2 is preferably less than or equal to about 170 sccm, and more preferably, less than or equal to about 120 sccm as shown in the graph y 3 . At this time, when the flow rate of N 2 becomes excessively low, the etching stop occurs.
  • the flow rate of N 2 is at least more than or equal to about 50 sccm. Resultantly, the flow rate of N 2 is preferably greater than or equal to about 50 sccm and less than or equal to about 170 sccm, and more preferably greater than or equal to about 80 sccm and less than or equal to about 120 sccm.
  • a ratio of the flow rate of N 2 to the flow rate of C 4 F 6 is preferably greater than or equal to about 50/16 and less than or equal to about 170/16 (i.e. greater than or equal to about 25/8 and less than or equal to about 85/8), and more preferably greater than or equal to about 80/16 and less than or equal to about 120/16 (i.e. greater than or equal to about 10/2 and less than or equal to about 15/2).
  • a ratio of the flow rate of gaseous mixture, which contains N 2 and O 2 , acting as the deposit removing gas to the flow rate of C 4 F 6 , acting as the etching gas is preferably greater than or equal to about 60/16 and less than or equal to about 180/16 (greater than or equal to about 15/4 and less than or equal to about 45/4), and more preferably greater than or equal to about 90/16 and less than or equal to about 130/16 (greater than or equal to about 45/8 and less than or equal to about 65/8).
  • a ratio of the flow rate of N 2 to the flow rate of O 2 is preferably greater than or equal to about 50/10 and less than or equal to about 170/10 (greater than or equal to about 5 and less than or equal to about 17), and more preferably greater than or equal to about 80/10 and less than or equal to about 120/10 (greater than or equal to about 8 and less than or equal to about 12).
  • the contact hole 210 may be formed in a self-aligning manner between the gates 202 while the silicon nitride film layer 204 , acting as the protective film layer of the gates 202 , is prevented from being etched as shown in FIG. 2B .
  • test results for the conventional etching method are presented for a comparison with the test results by the etching method in accordance with the present invention.
  • the conventional etching was conducted under conditions where the high frequency power applied to the upper electrode 122 was 1500 W at 60 MHz, the high frequency power (bias power) applied to the lower electrode 106 was about 1300 W at about 2 MHz, a flow rate ratio of C 5 F 8 /Ar/O 2 (a flow rate of C 5 F 8 /a flow rate of Ar/a flow rate of O 2 ) was about 16 sccm/800 sccm/18 sccm, temperatures of the lower and the upper electrodes in the processing chamber 104 were about 40° C.
  • He gas cooling gas
  • a back pressure gas applied to the center and edges of the backside of the wafer were about 5 Torr and 10 Torr, respectively.
  • the following results are average values of respective values measured at the center portion, at the intermediate portion between the end portion and the center portion, and at the end portion of the wafer W.
  • the etching rate of the silicon oxide film layer was about 500 nm/min, a removed amount t of the etched shoulder (edge) 204 a of the silicon nitride film layer 204 was about 8 nm. Additionally, the selectivity of the silicon oxide film layer 206 over the shoulder (edge) 204 a of the silicon nitride film layer 204 [the etching rate of the silicon oxide film layer/the etching rate of the shoulder (edge) of the silicon nitride film layer] was about 20.0.
  • the selectivity of the silicon oxide film layer 206 against the shoulder (edge) 204 a of the photoresist layer 208 was about 6.0.
  • N 2 is added to the processing gas to select the desired flow rate ratio, thereby preventing the etching stop from occurring and at the same time increasing the etching rate of the silicon oxide film layer 206 , acting as the protective film layer.
  • the silicon oxide film layer 206 acts as the protective film layer of the gates 202 . Therefore, the silicon nitride film layer 204 , acting as the protective film layer of the gates 202 , is prevented from being etched, thereby capable of forming the contact hole 210 with an improved aspect ratio.
  • silicon oxide film layer 206 as the silicon-containing oxide film acting as the insulating film layer in the present invention, however an inorganic low-k film, such as a carbon-added silicate (SiOC) film, a hydrogen-added silicate (SIOH) film and a fluorine-added silicate (SiOF) film, may be used instead of the silicon oxide film.
  • SiOC carbon-added silicate
  • SIOH hydrogen-added silicate
  • SiOF fluorine-added silicate
  • the silicon oxide film may be exemplified by a borophosphosilicate glass (BPSG) film, a phosphosilicate glass (PSG) film, a tetraethoxy orthosilane (TEOS) film, a thermal oxide (Th-OX) film or a spin on glass (SOG) film.
  • BPSG borophosphosilicate glass
  • PSG phosphosilicate glass
  • TEOS tetraethoxy orthosilane
  • Thi-OX thermal oxide
  • SOG spin on glass
  • C 4 F 6 gas is used as fluorocarbon-based gas which rendered to be included in the processing gas, but C 5 F 8 gas and the like may be used as the fluorocarbon-based gas.
  • the high frequency power with the frequency of about 60 Hz is applied to the upper electrode of the etching apparatus and the high frequency power with the frequency of about 2 MHz is applied to the lower electrode, however the present invention is not limited to what is explained above, and the high frequency power may be applied to the upper or the lower electrodes of the etching apparatus, or a magnetic field may be formed around the upper and/or the lower electrode.
  • the etching apparatus in which the high frequency power with the frequency of about 60 Hz is applied to the upper electrode and the high frequency power with the frequency of about 2 MHz is applied to the lower electrode, because the high frequency power applied to the upper electrode serves to control a plasma density and the high frequency power applied to the lower electrode functions to control an ion energy. Consequently, it is controllable, i.e., to attach and remove reaction products (deposits), affecting the etching selectivity.
  • the etching apparatus may be embodied by an ECR plasma etching apparatus, a helicon wave plasma etching apparatus, a TCP type plasma etching apparatus, and an inductively coupled plasma etching apparatus.
  • N 2 is added to the processing gas and the flow rate of N 2 is desirably selected to prevent the etching from stopping, to increase the etching rate of the silicon oxide film layer, acting as the insulating film layer, and to improve the etching selectivity of the silicon oxide film layer over the silicon nitride film layer, acting as the protective film layer of the gates. Therefore, the silicon nitride film, acting as the protective film layer of the gates, is prevented from being etched and the contact hole with the high aspect ratio may be stably formed securely while assuring an excellent controllability.

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US20160086814A1 (en) * 2013-04-19 2016-03-24 Tokyo Electron Limited Etching method
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US10501843B2 (en) 2013-06-20 2019-12-10 Applied Materials, Inc. Plasma erosion resistant rare-earth oxide based thin film coatings
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