IL137513A - Process for ashing an organic film from a substrate - Google Patents
Process for ashing an organic film from a substrateInfo
- Publication number
- IL137513A IL137513A IL13751399A IL13751399A IL137513A IL 137513 A IL137513 A IL 137513A IL 13751399 A IL13751399 A IL 13751399A IL 13751399 A IL13751399 A IL 13751399A IL 137513 A IL137513 A IL 137513A
- Authority
- IL
- Israel
- Prior art keywords
- ashing
- plasma
- photoresists
- sulfur trioxide
- group
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 62
- 238000004380 ashing Methods 0.000 title claims description 58
- 230000008569 process Effects 0.000 title claims description 51
- 239000000758 substrate Substances 0.000 title claims description 28
- 239000007789 gas Substances 0.000 claims description 59
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 56
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 23
- 229920002120 photoresistant polymer Polymers 0.000 claims description 20
- 239000000376 reactant Substances 0.000 claims description 16
- 230000000153 supplemental effect Effects 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 claims description 11
- 239000011368 organic material Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims description 6
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- QKCGXXHCELUCKW-UHFFFAOYSA-N n-[4-[4-(dinaphthalen-2-ylamino)phenyl]phenyl]-n-naphthalen-2-ylnaphthalen-2-amine Chemical compound C1=CC=CC2=CC(N(C=3C=CC(=CC=3)C=3C=CC(=CC=3)N(C=3C=C4C=CC=CC4=CC=3)C=3C=C4C=CC=CC4=CC=3)C3=CC4=CC=CC=C4C=C3)=CC=C21 QKCGXXHCELUCKW-UHFFFAOYSA-N 0.000 claims description 6
- WMIYKQLTONQJES-UHFFFAOYSA-N hexafluoroethane Chemical compound FC(F)(F)C(F)(F)F WMIYKQLTONQJES-UHFFFAOYSA-N 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 230000003287 optical effect Effects 0.000 claims description 4
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims description 4
- 229920005591 polysilicon Polymers 0.000 claims description 4
- 239000004065 semiconductor Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 3
- -1 aluminum-silicon-copper Chemical compound 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- LZDSILRDTDCIQT-UHFFFAOYSA-N dinitrogen trioxide Chemical compound [O-][N+](=O)N=O LZDSILRDTDCIQT-UHFFFAOYSA-N 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 3
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 239000003989 dielectric material Substances 0.000 claims description 2
- 238000010894 electron beam technology Methods 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 2
- 238000010884 ion-beam technique Methods 0.000 claims description 2
- 239000004973 liquid crystal related substance Substances 0.000 claims description 2
- 150000004767 nitrides Chemical class 0.000 claims description 2
- 239000001272 nitrous oxide Substances 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- 229920000620 organic polymer Polymers 0.000 claims description 2
- 125000002524 organometallic group Chemical group 0.000 claims description 2
- 239000003973 paint Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 239000010409 thin film Substances 0.000 claims description 2
- 235000012431 wafers Nutrition 0.000 claims description 2
- 229910000881 Cu alloy Inorganic materials 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000010408 film Substances 0.000 description 27
- 239000010410 layer Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 12
- 230000004913 activation Effects 0.000 description 11
- 238000001994 activation Methods 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 238000005530 etching Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000002939 deleterious effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008398 formation water Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000010849 ion bombardment Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- 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
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
-
- 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
- H01L21/31127—Etching organic layers
- H01L21/31133—Etching organic layers by chemical means
- H01L21/31138—Etching organic layers by chemical means by dry-etching
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/427—Stripping or agents therefor using plasma means only
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/26—Cleaning or polishing of the conductive pattern
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Plasma & Fusion (AREA)
- Drying Of Semiconductors (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
137513/2 PROCESS FOR ASHING AN ORGANIC FILM FROM A SUBSTRATE ANON, INC.
C: 38982 137513/2 PROCESS FOR ASHING ORGANIC MATERIALS FROM SUBSTRATES BACKGROUND OF THE INVENTION 1. Field of the Invention.
The present invention relates generally to the removal of organic materials on various substrates, and, more particularly, to an ashing method for removing organic films and materials temporarily formed on various substrate layers during fabrication of semiconductor, flat panel display, read/write heads, and other related devices. 2. Description of the Related Art.
Removal of the photoresist film is an important part of the process of fabricating semiconductor devices. The use of ashing methods, in particular, using a gas with high oxygen content, for removing organic films, such as resists and polyimides has been known for some time. The advances in plasma tools and the related processing techniques, over the last decade, have managed to keep up with the challenges of successive generations of Very Large Scale Integration (VLSI) and Ultra Large Scale Integration (ULSI) devices. However, as the size of the features and the thickness of films in these devices continue to decrease, the manufacturing challenges are also renewed with every generation of Integrated Circuits (ICs).
As the dramatic shrinking of IC geometries continues, the ashing methods are continuously faced with two problems: (a) achieving higher rates of residual-free resist removal and (b) lowering the amount of damage caused in the substrate layers underlying the resist film. These generally conflicting objectives are addressed by changing either the physical conditions of the plasma medium or the chemical conditions of the ashing process. For example, one can achieve higher rates of processing by either generating a dense plasma environment or by using or generating, in the plasma environment, chemical species that react more efficiently with the resist.
Substrate damage can likewise be attributed to both physical and chemical conditions of the plasma. For example, charging and ion bombardment effects are directly related to the physical properties of the plasma. Energetic ions can drive small quantities of heavy metal (i.e., Fe, Cu the resist films, into the substrate layer underneath the resist. The heavy metal contamination and in particular the subsequent permeation and migration of heavy metals into other substrates (e.g. silicon) layers can affect the minority carrier lifetime to the detriment of the device properties. Such bombardment effects become more severe as the resist films become thinner towards the end of the ashing process, particularly as the thickness of sensitive substrates are designed to be thinner.
Substrate damage also results from the chemical properties of plasma, such as etching or other poisonous effects on the layer underneath the resist. For example, etching of silicon oxide (Si02) occurs because of fluorine (F), when halogenated gas mixtures such as oxygen (02) and tetrafluoromethane (CF ) are used to increase the rate of plasma ashing. Similarly, energetic oxygen ions can contribute to the formation water inside the surface layers of spin-on-glass (SOG) films, resulting in an increase in the dielectric constant or in the related via-poisoning phenomenon.
These considerations apply, to various degrees depending on the application, to all conventional dry-etch plasma etchers, e.g., barrel, down-stream or parallel-electrode configurations, with the down-stream ashing being the most widely used method. To increase the processing rates and mmimize the problem of ion damage, techniques for higher plasma densities and lower ion energies may be employed. The new generations of advanced plasma sources achieve these objectives by decoupling the control of the plasma density from the control of ion energy in the plasma by such techniques as Electronic Cyclotron Resonance (ECR) or Inductively Coupled Plasma (ICP) in microwave or radio frequency power regimes. The art of these and other types of plasma technologies and plasma tools are well known and have been the subject of many US patents.
Independent of the nature and the regime of the plasma employed, the rate and completeness of ashing as well as any unwanted etching or damage to the substrate layer, in the conventional ashing tools, are strongly influenced by the chemical reactions between the resist and the substrate layer and the reactive ionic, neutral and radical species generated in the plasma. In a typical down-stream or other conventional asher, the nature of the plasma gas mixture is the pri-mary determinant of the ashing rate which is also sensitive to the "ashing temperature". The nature of the gas mixture also influences the activation energy of ashing which is a measure of the sensitivity of the ashing rate to the ashing temperature. 137513/2 The activation energy is obtained from the gradient of the Arrhenius plot which is a line plot of the ashing rate as a function of the inverse ashing temperatures. Therefore, a small activation energy (small slope of the Arrhenius plot) indicates that ashing rate is less sensitive to ashing temperature, and that the ashing process will be more stable and uniform. Lower activation energies also imply that the ashing temperature can be lowered without significant loss of ashing rate. This is particularly useful where VLSI or ULSI fabrication requires lower processing temperatures and yet where acceptable practical levels of ashing rates (i.e., 0.5 um/min) must be maintained.
A thorough discussion of ashing rates and activation energies for a series of gas mixtures consisting of one or more of the following: oxygen, hydrogen, nitrogen, water vapor and halogenide gases is given in the US Patent 4,961,820. It is shown that addition of nitrogen to oxygen plasma does not change the activation energy (0.52 eV for oxygen) and improves the rate of ashing only slightly (from 0.1 to 0.2 μιη/min at 160°C). However, addition of 5 to 10% hydrogen or water vapor to oxygen reduces the activation energy to about 0.4 eV with a similar improvement in the ashing rate as in the case of nitrogen addition. Addition of both nitrogen and 5 to 10% of either hydrogen or water vapor to oxygen plasma has a synergistic effect of increasing the ashing rate to a more practical level of 0.5 μπι/min (at 160°C).
The most dramatic improvements in the activation energy (down to 0.1 eV) and the ashing rate (>1.5 um min) are obtained when a halogenide (e.g., tetrafluoro-methane) is added to the oxygen plasma. However, in this case, CF4 also results in etching of such substrate layers as silicon oxide, polysilicon and aluminum due to fluorine reaction. It is reported that inclusion of water vapor in the reactant gas mixture will reduce the damage by CF4 apparently as a result of the reaction of water with CF4, thus suppressing the halogen action.
As seen from the above discussion, the search for a satisfactory reactant gas mixture, with reasonably high ashing rate and without any deleterious effect on the substrate layer underneath the resist film, continues. Furthermore, as the constraints of the VLSI and ULSI fabrication become more stringent, lower ashing temperatures and ashing-process stability (lower activation energy) increasingly become major requirements of a satisfactory reactant gas mixture.
The present inventors have successfully used anhydrous sulfur trioxide (SO3) in non-plasma resist removal applications at temperatures substantially lower than 200°C. Experiments have shown that exposure of resist-covered substrate surfaces to SO3 leaves polysilicon and metal substrates surfaces intact without any deleterious effect. Exposed silicon and metal surfaces are also protected because of passivation action of sulfur trioxide. Therefore, sulfur trioxide- plications. Particularly in the presence of oxygen plasma, it is expected that SO3 will enhance the oxygen radical formation, thus significantly improving the rate of the ashing reaction.
SUMMARY OF THE INVENTION It is an object of the present invention to provide an improved process for ashing organic materials, including photoresist residues, from substrates by including sulfur trioxide gas as a part of the reactive gas mix. This can be accomplished by employing one of three groups of gas mixes in the ashing process. These mixes include (1) Group 1 gas, which comprises only sulfur trioxide gas; (2) Group 2 gases, which comprise a mixture of sulfur trioxide and a supplemental gas such as water vapor, ozone, hydrogen, nitrogen, nitrogen oxides, or a halogenide such as tetrafluoro-methane (CF4), chlorine (Cl2), nitrogen trifluoride (NF3), hexafluoroethane (C2F6), or methyltrifluoride (CHF3); and (3) Group 3 gases, which comprise a mixture of sulfur trioxide and at least two of the foregoing supplemental gases.
As is well-known in the art, when certain of these supplemental gases are added to the main reactive ashing gas in the appropriate quantities and at the appropriate time in the process, they promote favorable ashing process characteristics and organic film removal performance. Such favorable characteristics and performance includes (a) higher ashing rates, (b) lower acti-vation energies, and (c) absence of ground layer etching during the organic removal process.
DESCRIPTION OF THE PREFERRED EMBODIMENTS Stripping and plasma ashing of organic photoresists, using one of the three groups of gases described above, are carried out with a conventional down-flow, barrel, downstream, direct, or other type of plasma ashing tool which is known in the prior art. The present invention pertains to the nature of the gases used in the ashing process and has application in all conventional ashing tools. The down-flow, barrel, direct, and downstream and other types of plasma ashing tools are well-known in this art and form no part of this invention.
The basic concept behind this invention is that sulfur trioxide gas, under the appropriate volumes and processing conditions, and with the optional addition of certain supplemental gases required to either reduce the activation energy, increase the speed of the ashing process, lower the operating temperature of the ashing process, or otherwise improve the effectiveness or efficiency wise react with, all types of organic coatings, films, layers and residues, including process- hardened photoresists, so as to cause them to be substantially removed, cleaned, or stripped from the surface of the substrate. In all embodiments of the present invention, the sulfur trioxide is provided in a source container from which sulfur trioxide gas is supplied to the processing chamber in the quantities and at the appropriate time in the ashing process. Within the source container, sulfur trioxide may be a mix of solid, liquid or gas, with the solid material in alpha form, beta form, gamma form or a mixture thereof.
Specifically, the following organic materials, in the form of coatings, films, layers, and residues, may be removed by the process of the present invention: polymerized and non-polymerized photoresists, photoresist residues, photosensitive and non-photosensitive organic compounds, paints, resins, multilayer organic polymers, organo-metallic complexes, sidewall polymers, and organic spin-on-glass. The photoresists may comprise positive optical photoresists, negative optical photoresists, electron beam photoresists, X-ray photoresists, and ion-beam photoresists.
Such coatings, films, layers, and residues may have been formed on a variety of substrates, including, but not limited to, (a) semiconductor wafers and devices comprised of silicon, polysilicon, germanium, III-V materials, and Π-VI materials, (b) oxides, (c) nitrides, (d) oxyni-trides, (e) inorganic dielectrics, (f) metals and metal alloys, (g) ceramic devices, (h) photomasks, (i) liquid crystal and flat panel displays, (j) printed circuit boards, (k) magnetic read/write heads, and (1) thin film heads.
The ashing process of the invention may be carried out at a temperature within the range of room temperature (about 20°C) up to 350°C. However, the ashing process is preferably carried out at as low a temperature as possible, consistent with maintaining as high an etching rate as possible. More preferably, then, the ashing process is carried out at a temperature less than about 200°C. 1. The First Embodiment.
One embodiment is a plasma ashing process conducted in any of the conventional down-flow, barrel, direct, and downstream and other types of ashing tools known in the prior art. In this first embodiment, the Group 1 gases are employed for the purpose of creating a plasma. In particular, the reactant gases comprise only sulfur trioxide. Sulfur trioxide is supplied to the plasma generating chamber, which is initially evacuated and exhausted to an appropriate vacuum. The supplied into the plasma generating chamber where a plasma is created with the reactant gases.
Active species which are generated as a plasma, flow down to a process chamber and come into contact with the organic film on the surface of the substrate by one of the methods disclosed in the prior art. As a result of the interaction of the organic film and the plasma, the organic film is either removed or chemically changed so as to render the film removable with subsequent rinsing or cleaning steps in the process. The process limitations, such as flow rate, microwave power, and the like are the same as those conventionally employed in the prior art, such as disclosed in U.S. Patents 4,669,689 and 4,961,820. 137513/2 2. The Second Embodiment.
Another embodiment of the present invention is a plasma ashing process conducted in any of the conventional down-flow, barrel, direct, and downstream and other types of ashing tools. In this second embodiment, the Group 2 gases are employed for the purpose of creating a plasma. In particular, the reactant gases comprise sulfur trioxide and one supplemental gas. Sulfur trioxide and the supplemental gas are supplied to the plasma generating chamber, which is initially evacuated and exhausted to an appropriate vacuum. The sulfur trioxide concentration in the Group 2 reactant gas is within the range of about 1 to 95 vol%. The supplemental gas comprises the balance (99 to 5 vol%).
The flow rate of each gas is controlled by a controller during the process. Microwave power is supplied into the plasma generating chamber where a plasma is created with the reactant gases. Active species which are generated as a plasma flow down to a process chamber and come into contact with the organic film on the surface of the substrate by one of the methods disclosed in the prior art. As a result of the interaction of the organic film and the plasma, the organic film is either removed or chemically changed so as to render the film removable with subsequent rinsing or cleaning steps in the process. As above, the process limitations, such as flow rate, microwave power, and the like are the same as those conventionally employed in the prior art.
The supplemental gas may comprise any of the gases selected from the group consisting of water vapor, ozone, hydrogen, nitrogen, nitrogen oxides, or a halogenide such as tetrafluoromethane (CF4), chlorine (Cl2), nitrogen trifluoride (NF3), hexafluoroethane (C F6), or methyltrifluoride (CHF3). Examples of nitrogen oxides include nitrous oxide (N20), nitric oxide (NO), nitrogen trioxide (N203), and nitrogen dioxide (N0 ). 3. The Third Embodiment.
Yet another embodiment of the present invention is a plasma ashing process conducted in any of the conventional down-flow, barrel, direct, and downstream and other types of ashing tools. In this third embodiments, the Group 3 gases are employed for the purpose of creating a plasma. In particular, the reactant gases comprise sulfur trioxide and at least two supplemental gases. Sulfur trioxide and the supplemental gases are supplied to the plasma generating chamber, which is initially evacuated and exhausted to an appropriate vacuum. The sulfur trioxide concentration in the Group 3 reactant gas is within the range of about 1 to 95 vol%. The supplemental gas comprises the balance (99 to 5 vol%). 137513/2 The flow rate of the gas is controlled by a controller during the process. Microwave power is supplied into the plasma generating chamber where a plasma is created with the reactant gases. Active species which are generated as a plasma, flow down to a process chamber and come into contact with the organic film on the surface of the substrate by one of the methods disclosed in the prior art. As a result of the interaction of the organic film and the plasma, the organic film is either removed, or chemically changed so as to render the film removable with subsequent rinsing or cleaning steps in the process. As above, the process limitations, such as flow rate, microwave power, and the like are the same as those conventionally employed in the prior art.
The supplemental gases comprise at least two of the gases from the list of supplemental gases given above.
In each of the foregoing embodiments, removal of organic films, including resist layers, is substantially complete, with little or no damage to the underlying ground layer.
Thus, there has been disclosed a process for removing organic materials from the surface of a substrate, employing a plasma ashing process that uses a reactant gas that contains sulfur trioxide. It will be readily apparent to those skilled in this art that various changes and modifications of an obvious nature may be made, and all such changes and modifications are considered to fall within the scope of the appended claims. 137513/2
Claims (13)
1. A process for removing an organic material from a surface of a substrate comprising the steps of: (a) creating a plasma from a reactant gas comprising sulfur trioxide and from 5 to 99 volume percent of at least one supplemental gas selected from the group consisting of water vapor, ozone, hydrogen, nitrogen, nitrogen oxides, and halogenides; and (b) allowing said plasma to impinge upon said surface of said substrate containing said organic material for a time sufficient to ash said organic material but insufficient to attack said surface of said substrate.
2. The process of claim 1, wherein said reactant gas consists essentially of sulfur trioxide gas.
3. The process of claim 1, wherein said reactant gas consists essentially of sulfur trioxide and one said supplemental gas, said sulfur trioxide having a concentration within a range of about 1 to 95 volume percent.
4. The process of claim 1, wherein said reactant gas consists essentially of sulfur trioxide and at least two said supplemental gases, said sulfur trioxide having a concentration within a range of about 1 to 95 volume percent.
5. The process of claim 1, wherein said nitrogen oxides are selected from the group consisting of nitrous oxide (N20), nitric oxide (NO), nitrogen trioxide (N2C ), and nitrogen dioxide (N02).
6. The process of claim 1, wherein said halogenides are selected from the group consisting of tetrafluoromethane (CF4), chlorine (Cl2), nitrogen trifluoride (NF3), hexafluoroethane (C2F6), and methyltrifluoride (CHF3). D-97034
7. ^ 7. The process of claim 1, wherein said organic material comprises a substance selected from the group consisting of polymerized and non-polymerized photoresists, photoresist residues, photosensitive and non-photosensitive organic compounds, paints, resins, multilayer organic polymers, organo-metallic complexes, sidewall polymers, and organic spin-on-glass.
8. The process of claim 7, wherein said photoresists are selected from the group consisting of positive optical photoresists, negative optical photoresists, electron beam photoresists, X- ray photoresists, and ion-beam photoresists.
9. The process of claim 1, wherein said substrate is selected from the group consisting of (a) semiconductor wafers and devices comprised of silicon, polysilicon, germanium, III-V materials, and II- VI materials, (b) oxides, (c) nitrides, (d) oxynitrides, (e) inorganic dielectrics, (f) metals and metal alloys, (g) ceramic devices, (h) photomasks, (i) liquid crystal and flat panel displays, (j) printed circuit boards, (k) magnetic read/write heads, and (I) thin film heads.
10. The process of claim 9, wherein said metals and metal alloys are selected from the group consisting of aluminum and aluminum-silicon-copper alloy.
11. The process of claim 1, wherein the plasma ashing process is carried out at a tem- perature between room temperature and 350°C.
12. The process of claim 11, wherein said temperature is less than 200°C.
13. The process of claim 1, wherein said process is carried out in a down-flow, barrel, downstream, or direct ashing apparatus. For the Applicant, Sariford T. Colb & Co. C: 38982
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US1469598A | 1998-01-28 | 1998-01-28 | |
| PCT/US1999/001560 WO1999039382A1 (en) | 1998-01-28 | 1999-01-26 | Process for ashing organic materials from substrates |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| IL137513A0 IL137513A0 (en) | 2001-07-24 |
| IL137513A true IL137513A (en) | 2004-05-12 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IL13751399A IL137513A (en) | 1998-01-28 | 1999-01-26 | Process for ashing an organic film from a substrate |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP1074043A4 (en) |
| JP (1) | JP3358808B2 (en) |
| KR (1) | KR100377711B1 (en) |
| CN (1) | CN1154159C (en) |
| CA (1) | CA2319018C (en) |
| IL (1) | IL137513A (en) |
| MY (1) | MY134851A (en) |
| TW (1) | TWI239994B (en) |
| WO (1) | WO1999039382A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6231775B1 (en) * | 1998-01-28 | 2001-05-15 | Anon, Inc. | Process for ashing organic materials from substrates |
| US20050136681A1 (en) * | 2003-12-23 | 2005-06-23 | Tokyo Electron Limited | Method and apparatus for removing photoresist from a substrate |
| KR100559947B1 (en) * | 2004-08-18 | 2006-03-13 | 동부아남반도체 주식회사 | Method for post treatment of metal wiring of semiconductor device |
| US7387968B2 (en) | 2005-11-08 | 2008-06-17 | Tokyo Electron Limited | Batch photoresist dry strip and ash system and process |
| US7381651B2 (en) * | 2006-03-22 | 2008-06-03 | Axcelis Technologies, Inc. | Processes for monitoring the levels of oxygen and/or nitrogen species in a substantially oxygen and nitrogen-free plasma ashing process |
| US8043434B2 (en) * | 2008-10-23 | 2011-10-25 | Lam Research Corporation | Method and apparatus for removing photoresist |
| CN104599962A (en) * | 2014-12-29 | 2015-05-06 | 上海华虹宏力半导体制造有限公司 | Thick aluminum etching polymer removing method |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59163826A (en) * | 1983-03-08 | 1984-09-14 | Toshiba Corp | Dry etching method |
| EP0368732B1 (en) * | 1988-11-04 | 1995-06-28 | Fujitsu Limited | Process for forming resist mask pattern |
| JPH0475323A (en) * | 1990-07-17 | 1992-03-10 | Seiko Epson Corp | Removal method of resist |
| US5037506A (en) * | 1990-09-06 | 1991-08-06 | Subhash Gupta | Method of stripping layers of organic materials |
| FR2673763A1 (en) * | 1991-03-06 | 1992-09-11 | Centre Nat Rech Scient | Method of anisotropic etching of polymers by plasma |
| JP3084910B2 (en) * | 1992-03-18 | 2000-09-04 | ヤマハ株式会社 | Wiring formation method |
| JPH05304089A (en) * | 1992-04-28 | 1993-11-16 | Dainippon Screen Mfg Co Ltd | Method and device of removing resist from surface of substrate |
| JP2572924B2 (en) * | 1992-09-04 | 1997-01-16 | 醇 西脇 | Surface treatment method of metal by atmospheric pressure plasma |
| US5550007A (en) * | 1993-05-28 | 1996-08-27 | Lucent Technologies Inc. | Surface-imaging technique for lithographic processes for device fabrication |
| JP3391410B2 (en) * | 1993-09-17 | 2003-03-31 | 富士通株式会社 | How to remove resist mask |
| US5824604A (en) * | 1996-01-23 | 1998-10-20 | Mattson Technology, Inc. | Hydrocarbon-enhanced dry stripping of photoresist |
| US5763016A (en) * | 1996-12-19 | 1998-06-09 | Anon, Incorporated | Method of forming patterns in organic coatings films and layers |
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1999
- 1999-01-26 KR KR10-2000-7008217A patent/KR100377711B1/en not_active IP Right Cessation
- 1999-01-26 CA CA002319018A patent/CA2319018C/en not_active Expired - Fee Related
- 1999-01-26 MY MYPI99000277A patent/MY134851A/en unknown
- 1999-01-26 JP JP2000529750A patent/JP3358808B2/en not_active Expired - Fee Related
- 1999-01-26 WO PCT/US1999/001560 patent/WO1999039382A1/en not_active Application Discontinuation
- 1999-01-26 CN CNB99802399XA patent/CN1154159C/en not_active Expired - Fee Related
- 1999-01-26 EP EP99904261A patent/EP1074043A4/en not_active Ceased
- 1999-01-26 IL IL13751399A patent/IL137513A/en not_active IP Right Cessation
- 1999-03-23 TW TW088101212A patent/TWI239994B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| IL137513A0 (en) | 2001-07-24 |
| WO1999039382A1 (en) | 1999-08-05 |
| CN1289452A (en) | 2001-03-28 |
| EP1074043A4 (en) | 2002-11-06 |
| JP2002502125A (en) | 2002-01-22 |
| CA2319018C (en) | 2004-08-24 |
| EP1074043A1 (en) | 2001-02-07 |
| TWI239994B (en) | 2005-09-21 |
| CA2319018A1 (en) | 1999-08-05 |
| CN1154159C (en) | 2004-06-16 |
| JP3358808B2 (en) | 2002-12-24 |
| MY134851A (en) | 2007-12-31 |
| KR20010040431A (en) | 2001-05-15 |
| KR100377711B1 (en) | 2003-03-26 |
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