Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/02—Inorganic compounds
  • C11D7/04—Water-soluble compounds
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P70/00—Cleaning of wafers, substrates or parts of devices
  • H10P70/20—Cleaning during device manufacture
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B81—MICROSTRUCTURAL TECHNOLOGY
  • B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
  • B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
  • B81C1/00841—Cleaning during or after manufacture
  • B81C1/00849—Cleaning during or after manufacture during manufacture
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B81—MICROSTRUCTURAL TECHNOLOGY
  • B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
  • B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
  • B81C1/00912—Treatments or methods for avoiding stiction of flexible or moving parts of MEMS
  • B81C1/0092—For avoiding stiction during the manufacturing process of the device, e.g. during wet etching
  • B81C1/00928—Eliminating or avoiding remaining moisture after the wet etch release of the movable structure
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
  • C08G18/4833—Polyethers containing oxyethylene units
  • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
  • C08G18/4841—Polyethers containing oxyethylene units and other oxyalkylene units containing oxyethylene end groups
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/02—Inorganic compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/22—Organic compounds
  • C11D7/26—Organic compounds containing oxygen
  • C11D7/261—Alcohols; Phenols
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/50—Solvents
  • C11D7/5004—Organic solvents
  • C11D7/5022—Organic solvents containing oxygen
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P70/00—Cleaning of wafers, substrates or parts of devices
  • H10P70/20—Cleaning during device manufacture
  • H10P70/23—Cleaning during device manufacture during, before or after processing of insulating materials
  • H10P70/234—Cleaning during device manufacture during, before or after processing of insulating materials the processing being the formation of vias or contact holes
• • A—HUMAN NECESSITIES
  • A46—BRUSHWARE
  • A46B—BRUSHES
  • A46B2200/00—Brushes characterized by their functions, uses or applications
  • A46B2200/10—For human or animal care
  • A46B2200/104—Hair brush
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2110/00—Foam properties
  • C08G2110/0083—Foam properties prepared using water as the sole blowing agent
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
  • C11D2111/10—Objects to be cleaned
  • C11D2111/14—Hard surfaces
  • C11D2111/22—Electronic devices, e.g. PCBs or semiconductors

Definitions

• compositions consisting of ammonia and an alkanol for avoiding pattern collapse when treating patterned materials with line-space dimensions of 50 nm or below.
• the present invention is directed to the use of a composition for manufacturing integrated circuits devices, optical devices, micromachines and mechanical precision devices, in particular for avoiding pattern collapse.
• patterned material layers like patterned photoresist layers, patterned barrier material layers containing or consisting of titanium nitride, tantalum or tantalum nitride, patterned multi-stack material layers containing or consisting of stacks e.g. of alternating polysilicon and silicon dioxide or silicon nitride layers, and patterned dielectric material layers containing or consisting of silicon dioxide or low-k or ultra- low-k dielectric materials are produced by photolithographic techniques.
• patterned material layers comprise structures of dimensions even below 22 nm with high aspect ratios.
• WO 2012/027667 A2 discloses a method of modifying a surface of a high aspect ratio feature by contacting the surface of the high aspect ratio feature with an additive composition to produce a modified surface, wherein forces acting on the high aspect ratio feature when a rinse solution is in contact with the modified surface are sufficiently minimized to prevent bending or collapse of the high aspect ratio feature at least during removal of the rinse solution or at least during drying of the high aspect ratio feature.
• solvents including isopropanol, but no esters are mentioned.
• TPGME 4-methyl-2-pentanol and tripropylene glycol methyl ether
• isopropanol and TPGME also combinations of solvents are disclosed.
• WO 2019/086374 A discloses a non-aqueous composition for anti pattern collapse cleaning comprising siloxane-type additives.
• the solvent essentially consists of one or more organic solvents, which may be protic or aprotic organic solvents.
• organic solvents which may be protic or aprotic organic solvents.
• Preferred are one or more polar protic organic solvents, most preferred are single polar protic organic solvents like isopropanol.
• WO 2019/224032 A discloses a non-aqueous composition for anti pattern collapse cleaning comprising a Ci to Ob alkanol and a carboxylic acid ester for treating substrates comprising patterns having line-space dimensions with a line width of 50 nm or below and aspect ratios of 4 and more.
• US 2017/17008 A discloses a pattern treatment composition comprising a polymer comprising a surface attachment group for forming a bond with the surface of the patterned feature and a solvent and a second a pattern treatment composition that is different from the first one.
• the solvents may be a combination of n-butylacetate and isopropanol.
• Unpublished European patent application No. 19168153.5 discloses a non-aqueous composition for treating substrates having patterned material layers having line-space dimensions with a line width of 50 nm or below, aspect ratios of greater or equal 4 or a combination thereof comprising an organic protic solvent, ammonia, and a non-ionic H-silane additive.
• compositions either still suffer from high pattern collapse in sub 50 nm, particularly sub 22 nm structures, or troublesome residues of non-volatile additives remain on the surface of the structured substrates to be treated.
• the compounds according to the present invention shall allow for the chemical rinse of patterned material layers comprising patterns with a high aspect ratio and line-space dimensions with a line width of 50 nm and less, in particular, of 32 nm and less, especially, of 22 nm and less, without causing pattern collapse.
• a Ci to C 4 alkanol for anti-pattern collapse treatment of a substrate comprising patterned material layers having line-space dimensions with a line width of 50 nm or below, aspect ratios of greater or equal 4, or a combination thereof.
• Another embodiment of the present invention is a method for manufacturing integrated circuit devices, electronic data storage devices, optical devices, micromachines and mechanical precision devices, the said method comprising the steps of
• composition according to the present invention are particularly useful for avoiding pattern collapse of non-photoresist patterns with high aspect ratios stacks (HARS).
• HTS aspect ratios stacks
• the present invention is directed to the use of a composition particularly for manufacturing patterned materials comprising sub 50 nm sized features like integrated circuit (IC) devices, data storage devices, optical devices, micromachines and mechanical precision devices, in particular IC devices.
• the composition is also referred to herein as “anti pattern collapse composition” or, since ammonia is essentially dissolved in the Ci to C 4 alkanol, simply “APCC solution”.
• the substrate is a semiconductor substrate, more preferably a silicon wafer, which wafers are customarily used for manufacturing IC devices, in particular IC devices comprising ICs having LSI, VLSI and ULSI.
• patterned material layer refers to a layer supported on a substrate.
• the supported layer has a specific pattern preferably having line-space structures with a line width of 50 nm and below wherein the supporting substrate is typically a semiconductor substrate, e.g., a semiconductor wafer.
• Such line space structures may be but are not limited to pillars and lines.
• “Width” herein means the shortest distance from one end to the other end of a structure, e.g. 30 nm for a 30 nm c 50 nm pillar or 30 nm c 1000 nm line; or 40 nm for a pillar with a diameter of 40 nm.
• patterned material layer having line-space dimensions with a line width of 50 nm or below means that the patterned material comprises line-space structures with a line width of 50 nm but also line space structures with a line width smaller (narrower) than 50 nm.
• the ratio of the line width to the width of space between two adjacent lines is preferably lower than 1:1, more preferably lower than 1:2. Patterned material layers having such a low “line-width-to-space-width” ratio are known by the skilled person to require a very delicate handling during production.
• the APCC solution is particularly suitable for treating substrates having patterned material layers having line-space dimensions with a line width of 50 nm and less, in particular, 32 nm and less and, especially, 22 nm and less, i.e. patterned material layers for the sub-22 nm technology nodes.
• the patterned material layers preferably have aspect ratios above 4, preferably above 5, more preferably above 6, even more preferably above 8, even more preferably above 10, even more preferably above 12, even more preferably above 15, even more preferably above 20.
• the critical aspect ratio also depends on the substrate to be treated for anti pattern collapse. For example, since low-k dielectrics are more unstable and tend to collapse aspect ratios of 4 are already challenging.
• the composition comprises ammonia in an amount of from 0.1 to 3 % by weight.
• the amount of ammonia is of from 0.2 to 2.8 % by weight, particularly of from 0.3 to 2.7 % by weight, more particularly of from 0.5 to 2.5 % by weight, even more particularly of from 0.8 to 2.2 % by weight, most particularly of from 1.0 to 2.0 % by weight.
• APCC compositions having the desired ammonia concentration fixed stock solutions are available in the market, e.g. a solution of 4% ammonia in I PA (available from TCI) or a 7N solution of ammonia in methanol (available from Acros), or may be prepared by bubbling ammonia through the respective solvent until the desired concentration is reached. The ammonia concentration may then be adjusted as desired by adding respective amounts of the respective solvent.
• the composition comprises a Ci to C 4 alkanol (also referred to as “alkanol”). It is possible to use more than one, e.g. two or three, Ci to C 4 alkanols but it is preferred to use only one Ci to C 4 alkanol.
• the alkanol is methanol, ethanol, 1-propanol or 2-propanol or mixtures thereof. Particularly preferred are methanol, 2-propanol, or mixtures thereof. Most particularly preferred is 2-propanol.
• the content of the Ci to C 4 alkanol in the composition is from 98 % by weight to 99.9 % by weight and sums up with ammonia to 100 % by weight of the composition.
• composition essentially consists of ammonia and the alkanol.
• “essentially consisting of” means that the content of other components does not influence the anti pattern collapse rate and characteristics of the composition. Depending on the nature of the other components this means that its content should be below 1 % by weight, preferably below 0.5% by weight, more preferably below 0.1% by weight, most preferably below 0.01% by weight.
• the anti pattern collapse cleaning (APCC) composition consists of the alkanol and ammonia essentially dissolved therein.
• composition is a homogeneous (one phase) composition.
• the composition is non-aqueous.
• “non-aqueous” means that the composition may only contain low amounts of water up to about 1 % by weight.
• the non-aqueous composition comprises less than 0.5 % by weight, more preferably less than 0.2 % by weight, even more preferably less than 0.1 % by weight, even more preferably less than 0.05 % by weight, even more preferably less than 0.02 % by weight, even more preferably less than 0.01 % by weight, even more preferably less than 0.001 % by weight.
• Most preferably essentially no water is present in the composition.
• “Essentially” here means that the water present in the composition does not have a significant influence on the performance of the additive in the non-aqueous composition with respect to pattern collapse of the substrates to be treated.
• composition according to the present invention may be applied to substrates of any patterned material as long as structures tend to collapse due to their geometry.
• the patterned material layers may be any suitable material layers.
• the patterned material layers may be any suitable material layers.
• patterned multi-stack material layers containing or consisting of layers of at least two different materials selected from the group consisting of silicon, polysilicon, low-k and ultra-low-k materials, high-k materials, semiconductors other than silicon and polysilicon, and metals, and d) patterned dielectric material layers containing or consisting of low-k or ultra-low-k dielectric materials.
• composition according to the invention it is particularly preferred to apply the composition according to the invention to patterned silicon layers.
• the method for manufacturing integrated circuit devices, electronic data storage devices, optical devices, micromachines and mechanical precision devices comprises the steps described below.
• a substrate having patterned material layers having line-space dimensions with a line width of 50 nm or below, aspect ratios of greater or equal 4, or a combination thereof is provided.
• the substrate is preferably provided by a photolithographic process comprising the steps of
• any customary and known immersion photoresist, EUV photoresist or eBeam photoresist can be used.
• the immersion photoresist may already contain at least one of the siloxane additives or a combination thereof. Additionally, the immersion photoresist may contain other nonionic additives. Suitable nonionic additives are described, for example, in US 2008/0299487 A1, page 6, paragraph [0078] Most preferably, the immersion photoresist is a positive resist. Beside e-Beam exposure or extreme ultraviolet radiation of approx. 13.5 nm, preferably, UV radiation of the wavelength of 193 nm is used as the actinic radiation.
• ultra-pure water is used as the immersion liquid.
• TMAH tetramethylammonium hydroxide
• Customary and known equipment customarily used in the semiconductor industry can be used for carrying out the photolithographic process in accordance with the method of the invention.
• step (b) the substrate is contacted with an aqueous pretreatment composition comprising or essentially consisting of 0.1 to 2 % by weight HF, preferably 0.25 to 1 % by weight HF.
• the pretreatment composition consists of water and HF.
• the pretreatment is usually performed for about 10 s to about 10 min, more preferably from about 20 s to about 5 min, most preferably from about 30 s to about 3 min.
• step (c) the pretreatment composition of step (b) is removed from the substrate. This is usually done by rinsing the substrate with ultrapure water. Preferably this step is preferably performed once, but may also be repeated, if required.
• step (d) the substrate is contacted with a solvent-based composition essentially consisting of the APCC solution described herein.
• This APCC treatment is usually performed for about 10 s to about 10 min, more preferably from about 20 s to about 5 min, most preferably from about 30 s to about 3 min.
• all steps (a) to (d) may be used at any temperature from 10 to 40 °C or higher. If the temperature is higher, the compositions are not stable since the amount of ammonia will be quickly reduced by evaporation. A lower temperature is generally possible but would require intensive cooling. It is preferred that the temperature is from 10 to 35 °C, even more preferred from 15 to 30 °C.
• step (e) the solution is removed from the substrate. Any known methods customarily used for removing liquids from solid surfaces can be employed. In a preferred embodiment this is done by
• a polar protic solvent preferably a Ci to C 4 alkanol, most preferably with 2-propanol, methanol or ethanol;
• step (ii) evaporating the polar protic solvent of step (i), preferably in the presence of an inert gas.
• an inert gas is nitrogen.
• ammonia in methanol solution of desired concentrations desired amounts of a 7N stock solution of ammonia in methanol (available from Acros) were added to the beaker first. Methanol was then added to make a solution of 100g in total. The solution was then stirred at 300 rpm for at least 3 minutes prior to use.
• Patterned silicon wafers with a circular nano pillar pattern were used to determine the pattern collapse performance of the formulations during drying.
• the (aspect ratio) AR 20 pillars used for testing had a height of 600 nm and a diameter of 30 nm.
• the pitch size was 90 nm. 1x1 cm wafer pieces where processed in the following sequence without drying in between:
• Table 1 shows that example compositions 2 to 6 and 8 to 10 show a beneficial effect on the degree of pattern collapse compared to the composition with 2-propanol or methanol only.
• Comparative Examples 11 and 12 show some comparative experiments a with a solvent based anti pattern collapse composition according to WO 2019/224032 A.
• the compositions according to the present invention comprising ammonia show much higher rate of uncollapsed pillars than those of WO 2019/224032 A.

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• 2021
  • 2021-05-12 CN CN202180037457.8A patent/CN115668447A/zh active Pending
  • 2021-05-12 EP EP21724690.9A patent/EP4158678A1/en active Pending
  • 2021-05-12 IL IL298441A patent/IL298441A/en unknown
  • 2021-05-12 US US17/999,734 patent/US20230235252A1/en active Pending
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