CN107978511A - The forming method of oxide layer and semiconductor devices - Google Patents

The forming method of oxide layer and semiconductor devices Download PDF

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Publication number
CN107978511A
CN107978511A CN201711160590.4A CN201711160590A CN107978511A CN 107978511 A CN107978511 A CN 107978511A CN 201711160590 A CN201711160590 A CN 201711160590A CN 107978511 A CN107978511 A CN 107978511A
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China
Prior art keywords
substrate
solution
oxide layer
forming method
oxide
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Pending
Application number
CN201711160590.4A
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Chinese (zh)
Inventor
蔡松柏
李侃
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Wuhan Xinxin Semiconductor Manufacturing Co Ltd
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Wuhan Xinxin Semiconductor Manufacturing Co Ltd
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Priority to CN201711160590.4A priority Critical patent/CN107978511A/en
Publication of CN107978511A publication Critical patent/CN107978511A/en
Pending legal-status Critical Current

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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
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
    • H01L21/02299—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment
    • H01L21/02301—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment in-situ cleaning
    • 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
    • H01L21/02041—Cleaning
    • H01L21/02057—Cleaning during device manufacture
    • 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
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/02164—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon oxide, e.g. SiO2
    • 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
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Cleaning Or Drying Semiconductors (AREA)

Abstract

The present invention provides a kind of oxide layer and the forming method of semiconductor devices, the substrate is cleaned using the first solution first, to remove the particle of the substrate surface and organic substance, substrate is exposed, easy to follow-up oxidation, substrate described in the second solution oxide is used again, to form oxide layer over the substrate, since the concentration of hydrogen peroxide in second solution is big, oxidisability is strong, can be the surface oxidation of substrate be formed a fine and close oxide layer in the short time, furthermore, second solution can be evenly distributed on substrate, the oxide layer uniformity formed using the second solution oxide is more preferable, and, substrate is cleaned and aoxidized respectively using the first solution and the second solution and can be completed in same board, board need not be replaced, manufacturing time and cost are saved.

Description

The forming method of oxide layer and semiconductor devices
Technical field
The present invention relates to field of semiconductor manufacture, more particularly to a kind of oxide layer and the forming method of semiconductor devices.
Background technology
In field of semiconductor manufacture, silica, which has, to be extremely widely applied, it can both be used as metal oxide half The grid oxic horizon of conductor field-effect tube (MOSFET), can also as the insulating medium layer between semiconductor devices, also, In non-volatile semiconductor memory, silica is also used to form tunnel oxide.With semiconductor fabrication Constantly progressive, the requirement for oxide layer manufacturing process is also higher and higher.
The existing method for forming oxide layer normally results in the in uneven thickness of the oxide layer of substrate surface The oxidated layer thickness of edges of substrate part is more than the oxidated layer thickness of substrate center part), this will cause the electricity of semiconductor devices Learn performance to change, and then cause the yield of product to decline.
The content of the invention
It is an object of the invention to provide a kind of forming method of oxide layer, to solve the oxidation formed in the prior art The problems such as layer lack of homogeneity.
In order to achieve the above object, the present invention provides a kind of forming method of oxide layer, for forming oxygen on substrate Change layer, including：
Substrate is provided；
The first solution is used to clean the substrate to expose silicon face, first solution includes peroxide Change hydrogen；
Using substrate described in the second solution oxide, to form oxide layer over the substrate, second solution includes Hydrogen peroxide, the concentration of hydrogen peroxide is high in concentration first solution of hydrogen peroxide in second solution；
The surface of the substrate is cleaned using deionized water.
Optionally, before being cleaned using the first solution to the substrate, the forming method of the oxide layer is also wrapped Include：
The substrate is cleaned using hydrofluoric acid solution, to remove the oxide layer of self-assembling formation on the substrate；
The substrate is cleaned using deionized water, to remove remaining hydrofluoric acid solution on the substrate.
Optionally, the concentration of the hydrofluoric acid solution is 0.2wt%-0.8wt%, and temperature is Celsius for 18 degree Celsius -50 Degree.
Optionally, first solution is the mixed solution of ammonium hydroxide, hydrogen peroxide and deionized water.
Optionally, the concentration ratio of ammonium hydroxide, hydrogen peroxide and deionized water is 1 in first solution:1:5-1:1: 7, temperature is 30 degrees Celsius -50 degrees Celsius.
Optionally, second solution is the mixed solution of hydrochloric acid, hydrogen peroxide and deionized water.
Optionally, the concentration ratio of hydrochloric acid, hydrogen peroxide and deionized water is 1 in second solution:1:6-1:2:8, temperature Spend for 30 degrees Celsius -50 degrees Celsius.
Optionally, the surface clean 1min-3min using deionized water to the substrate, and using described in nitrogen drying Substrate.
Optionally, the thickness of the oxide layer is 15 angstroms -35 angstroms.
Present invention also offers a kind of forming method of semiconductor devices, formed using the forming method of the oxide layer One oxide layer.
In the forming method of oxide layer provided by the invention, the substrate is cleaned using the first solution first, To remove the particle of the substrate surface and organic substance, substrate is exposed, easy to follow-up oxidation, then using second Substrate described in solution oxide, to form oxide layer over the substrate, due to the concentration of hydrogen peroxide in second solution Greatly, oxidisability is strong, can with the short time by the surface oxidation of substrate to form a fine and close oxide layer, furthermore, the second solution can To be evenly distributed on substrate, the oxide layer uniformity formed using the second solution oxide is more preferable, also, molten using first Liquid and the second solution, which are cleaned and aoxidized to substrate respectively, to be completed in same board, it is not necessary to replaced board, saved About manufacturing time and cost.
Brief description of the drawings
Fig. 1 is the flow chart of the forming method for the oxide layer that embodiment provides；
Fig. 2-Fig. 4 is the diagrammatic cross-section of the semiconductor structure formed using the forming method of the oxide layer；
Wherein, 1- substrates, 12- natural oxidizing layers, 13- oxide layers.
Embodiment
The embodiment of the present invention is described in more detail below in conjunction with schematic diagram.According to description below And claims, advantages and features of the invention will become apparent from.It should be noted that attached drawing is using very simplified form And non-accurate ratio is used, only for the purpose of facilitating and clarifying the purpose of the embodiments of the invention.
Refering to Fig. 1, the flow chart of the forming method of its oxide layer provided for embodiment, the formation side of the oxide layer Method is used to form oxide layer on substrate, including：
S1：Substrate is provided；
S2：The first solution is used to clean the substrate to expose silicon face, first solution included Hydrogen oxide；
S3：Using substrate described in the second solution oxide, to form oxide layer over the substrate, in second solution Including hydrogen peroxide, the concentration of hydrogen peroxide is high in the concentration of hydrogen peroxide first solution in second solution；
S4：The surface of the substrate is cleaned using deionized water.
In the forming method of oxide layer provided by the invention, the substrate is cleaned using the first solution first, To remove the particle of the substrate surface and organic substance, substrate is exposed, easy to follow-up oxidation, then using second Substrate described in solution oxide, to form oxide layer over the substrate, due to the concentration of hydrogen peroxide in second solution Greatly, oxidisability is strong, can with the short time by the surface oxidation of substrate to form a fine and close oxide layer, furthermore, the second solution can To be evenly distributed on substrate, the oxide layer uniformity formed using the second solution oxide is more preferable, also, molten using first Liquid and the second solution, which are cleaned and aoxidized to substrate respectively, to be completed in same board, it is not necessary to replaced board, saved About manufacturing time and cost.
Next, the forming method of oxide layer provided by the invention will be further described with reference to Fig. 2-Fig. 4.It is first First, referring to Fig. 2, providing substrate 1, the substrate 1 can be silicon substrate, naturally it is also possible to be germanium substrate, germanium silicon substrate or exhausted Silicon etc. on edge body.
The substrate 1 is cleaned using hydrofluoric acid solution (HF), the time of cleaning is less than or equal to 40s, the hydrogen Natural oxidizing layer (the SiO of fluorspar acid solution and substrate surfacex) generation SiF4, to remove the natural oxidizing layer 11 on 1 surface of substrate, with The silicon face on substrate 1 is exposed (if not silicon substrate, can use and deposit a silicon material layer on 1 surface of substrate, or adopt Silicon material layer is formed with epitaxy technology), the concentration of the hydrofluoric acid solution is 0.2wt%-0.8wt%, and temperature is Celsius for 18 - 50 degrees Celsius of degree, is, for example, 20 degrees Celsius, 30 degrees Celsius and 40 degrees Celsius.Substrate surface is that growth is high without natural oxidizing layer The key of pure and mild super thin oxide layer (thickness is less than or equal to 50 angstroms), the substrate 1 after being cleaned by hydrofluoric acid solution, surface are natural Oxide 11 is removed, also, 1 surface of substrate crossed through hydrofluoric acid treatment is terminated by hydrogen atom completely, makes the surface of substrate 1 The state identical with body silicon crystal is remain, so there is very strong stability in atmosphere, avoids and reoxidizes.
Substrate 1 described in deionized water rinsing is used again, to remove the hydrofluoric acid solution of 1 surface residual of substrate.Due to The surface that hydrofluoric acid in previous step remains in substrate 1 will influence whether the formation of subsequent oxidation layer, it is therefore desirable to using going Ionized water removes the hydrofluoric acid clean on surface.The time of deionized water rinsing substrate to be measured is used as 1min-3min, preferably For 2min, the hydrofluoric acid on 1 surface of substrate can be removed completely.
Then, refering to Fig. 3, cleaning 50s-100s carries out the substrate 1 using the first solution, in first solution Including the relatively low hydrogen peroxide of concentration, for example, first solution can be ammonium hydroxide, hydrogen peroxide and deionized water (NH4OH/H2O2/H2O mixed solution), these three chemicals press 1:1:5 to 1:1:7 proportioning mixing, wherein H2O2Concentration It is, for example, 1wt%, 1.5wt% and 2wt% for 0.5wt%-2.5wt%.First solution alkaline, can remove 1 surface of substrate Particle and organic substance.The first solution comprising low concentration hydrogen peroxide, can divide and dissolved particles, destroy particle with Adhesive force between substrate 1, makes particle depart from substrate surface, and the oxidation effect of hydrogen peroxide also causes the surface of substrate 1 A protective film is formd, prevents particle from being adhered to the surface of substrate 1 again.The temperature of first solution for 30 degrees Celsius- 50 degrees Celsius, be, for example, 35 degrees Celsius, 40 degrees Celsius and 45 degrees Celsius.
Referring to Fig. 4, substrate 50s-100s described in the second solution oxide is used again, described in being formed on the substrate 1 Oxide layer 12, second solution include hydrogen peroxide, also, in second solution hydrogen peroxide concentration it is more described The concentration of hydrogen peroxide is high in first solution so that second solution has a stronger oxidisability, and second solution can be with For hydrochloric acid, hydrogen peroxide and deionized water (HCl/H2O2/H2O mixed solution), these three chemicals press 1:1:6 to 1:2:8 Proportioning mixing, wherein H2O2Concentration be 1wt%-3wt%, be, for example, 1.5wt%, 2wt% and 2.5wt%.In second solution H2O2Concentration is big, and oxidisability is strong, 1 surface oxidation of substrate can be formed 12 (SiO of oxide layerx), due to H2O2Strong oxdiative Property, therefore the consistency of the oxide layer 12 in 1 Surface Creation of substrate is high.
Preferably, the formation for the method progress oxide layer 12 that substrate 1 is immersed in the second solution, substrate table can be used Face 1 is completely immersed in the second solution, and the oxidation reaction speed of 1 surface of substrate everywhere is roughly the same, so the oxide layer 12 formed Thickness it is uniform.The temperature of second solution is, for example, 35 degrees Celsius, 40 degrees Celsius and 45 at 30 degrees Celsius -50 degrees Celsius Degree Celsius.The thickness of the oxide layer 12 is 15 angstroms -35 angstroms, is, for example, 20 angstroms, 25 angstroms and 30 angstroms.Certainly, in the present embodiment The thickness of oxide layer 12 is not limited thereto, also can be according to actual device needs, the corresponding thickness for adjusting oxide layer 12.
Further, it is molten using the second of high concentration at high temperature for a long time since the second solution is a kind of strong oxidizer Liquid can bring potential danger to operating personnel and line of production technology.Used by the present embodiment the second solution oxide when Between it is short, so as to reduce the danger brought due to long-time using the second solution.It can also use the method for heating water bath will Second solution is heated to required temperature, and than direct-fired method, its process heated more relaxes, and the second solution Phenomena such as being thermally equivalent in a reservoir, producing splash due to hot-spot, be more conducive to and improve technological operation Security.
Substrate 1 described in deionized water rinsing is finally used, to remove the second solution of 1 surface residual of substrate.Using Time with deionized water rinsing substrate to be measured is 1min-3min, is preferably 2min, can be molten by the second of 1 surface of substrate Liquid all washes away.The substrate is dried up using nitrogen again, the time of the drying employed in the present embodiment is 40s to 2min, excellent Elect 1min as.It is understood that from the formation for being removed to oxide layer 12 of 1 surface natural oxidizing layer 11 of substrate, all steps Can in same board into, avoid replace board caused by time and cost waste, saved manufacturing time and Cost.
Present invention also offers a kind of forming method of semiconductor devices, formed using the forming method of the oxide layer One oxide layer.
To sum up, in oxide layer provided by the invention and the forming method of semiconductor devices, first using the first solution pair The substrate is cleaned, and to remove the particle of the substrate surface and organic substance, substrate is exposed, easy to follow-up Oxidation, then using substrate described in the second solution oxide, to form oxide layer over the substrate, due to second solution The concentration of middle hydrogen peroxide is big, and oxidisability is strong, can be the surface oxidation of substrate is formed a fine and close oxidation in the short time Layer, furthermore, the second solution can be evenly distributed on substrate, using the second solution oxide formed oxide layer uniformity more Well, also, substrate is cleaned and aoxidized respectively using the first solution and the second solution can be complete in same board Into, it is not necessary to board is replaced, has saved manufacturing time and cost.
The preferred embodiment of the present invention is above are only, does not play the role of any restrictions to the present invention.Belonging to any Those skilled in the art, in the range of technical scheme is not departed from, to the invention discloses technical solution and Technology contents make the variation such as any type of equivalent substitution or modification, belong to the content without departing from technical scheme, still Belong within protection scope of the present invention.

Claims (10)

  1. A kind of 1. forming method of oxide layer, it is characterised in that including：
    Substrate is provided；
    The first solution is used to clean the substrate to expose silicon face, first solution includes hydrogen peroxide；
    Using substrate described in the second solution oxide, to form oxide layer over the substrate, second solution includes peroxide Change hydrogen, the concentration of hydrogen peroxide is high in concentration first solution of hydrogen peroxide in second solution；
    The surface of the substrate is cleaned using deionized water.
  2. 2. the forming method of oxide layer as claimed in claim 1, it is characterised in that using No.1 standard cleaning liquid to the lining Before bottom is cleaned, the forming method of the oxide layer further includes：
    The substrate is cleaned using hydrofluoric acid solution, to remove the oxide layer of self-assembling formation on the substrate；
    The substrate is cleaned using deionized water, to remove remaining hydrofluoric acid solution on the substrate.
  3. 3. the forming method of oxide layer as claimed in claim 2, it is characterised in that the concentration of the hydrofluoric acid solution is 0.2wt%-0.8wt%, temperature are 18 degrees Celsius -50 degrees Celsius.
  4. 4. the forming method of oxide layer as claimed in claim 1, it is characterised in that first solution is ammonium hydroxide, mistake The mixed solution of hydrogen oxide and deionized water.
  5. 5. the forming method of oxide layer as claimed in claim 4, it is characterised in that ammonium hydroxide, mistake in first solution The concentration ratio of hydrogen oxide and deionized water is 1:1:5-1:1:7, temperature is 30 degrees Celsius -50 degrees Celsius.
  6. 6. the forming method of oxide layer as claimed in claim 1, it is characterised in that second solution is hydrochloric acid, peroxidating The mixed solution of hydrogen and deionized water.
  7. 7. the forming method of oxide layer as claimed in claim 6, it is characterised in that hydrochloric acid, peroxidating in second solution The concentration ratio of hydrogen and deionized water is 1:1:6-1:2:8, temperature is 30 degrees Celsius -50 degrees Celsius.
  8. 8. the forming method of oxide layer as claimed in claim 1, it is characterised in that the table using deionized water to the substrate 1min-3min is cleaned in face, and dries up the substrate using nitrogen.
  9. 9. the forming method of oxide layer as claimed in claim 1, it is characterised in that the thickness of the oxide layer is 15 angstrom -35 Angstrom.
  10. 10. a kind of forming method of semiconductor devices, it is characterised in that use oxygen as claimed in any one of claims 1-9 wherein The forming method for changing layer forms an oxide layer.
CN201711160590.4A 2017-11-20 2017-11-20 The forming method of oxide layer and semiconductor devices Pending CN107978511A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112652518A (en) * 2019-10-11 2021-04-13 中芯国际集成电路制造（天津）有限公司 Method for forming semiconductor device

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103918090A (en) * 2011-10-07 2014-07-09 Jet股份有限公司 Method for manufacturing solar cell
CN104143590A (en) * 2014-08-08 2014-11-12 中国科学院宁波材料技术与工程研究所 Simple and fast silicon surface passivation method
CN104882362A (en) * 2015-05-25 2015-09-02 上海华力微电子有限公司 Oxygen ambient silica layer cleaning process and method for removing photoetching residues before trap injection
CN105609408A (en) * 2015-12-23 2016-05-25 上海华虹宏力半导体制造有限公司 Forming method of semiconductor device
CN106033711A (en) * 2015-03-18 2016-10-19 联华电子股份有限公司 Cleaning method of substrate

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103918090A (en) * 2011-10-07 2014-07-09 Jet股份有限公司 Method for manufacturing solar cell
CN104143590A (en) * 2014-08-08 2014-11-12 中国科学院宁波材料技术与工程研究所 Simple and fast silicon surface passivation method
CN106033711A (en) * 2015-03-18 2016-10-19 联华电子股份有限公司 Cleaning method of substrate
CN104882362A (en) * 2015-05-25 2015-09-02 上海华力微电子有限公司 Oxygen ambient silica layer cleaning process and method for removing photoetching residues before trap injection
CN105609408A (en) * 2015-12-23 2016-05-25 上海华虹宏力半导体制造有限公司 Forming method of semiconductor device

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112652518A (en) * 2019-10-11 2021-04-13 中芯国际集成电路制造（天津）有限公司 Method for forming semiconductor device

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Application publication date: 20180501