CN107797378A - The forming method of graphene layer - Google Patents

Abstract

A kind of forming method of graphene layer includes：In the first substrate depositing first material layer；And the deposited graphite alkene layer on the first material layer.Methods described also includes：The deposition of amorphous silicon layers on the graphene layer；And the amorphous silicon layer is bound to the second substrate, so as to form component.Methods described also includes：The component is set to anneal, so as to which the amorphous silicon layer is transformed into silicon oxide layer.The forming method of the graphene layer also includes：From the first substrate described in the assembly removal；And from first material layer described in the assembly removal, so as to expose the graphene layer.

Description

The forming method of graphene layer

Technical field

Embodiments of the invention are related to a kind of forming method of graphene layer.

Background technology

Higher device density, higher performance and more inexpensive nanometer technology are pursued as semiconductor industry proceeds to, Tightened up requirement is proposed to the lithography tool used in semiconductor manufacturing.Such as extreme ultraviolet (extreme is utilized Ultraviolet, EUV) technology such as photoetching supports the critical dimension (critical of smaller integrated circuit (IC) device Dimension, CD) demand.Extreme ultraviolet photolithographic uses the extreme ultraviolet that wavelength is about 1 nanometer to 100 nanometers (such as 13.5 nanometers) Radiation in area, the ripple in wavelength ratio deep ultraviolet (deep ultraviolet, the DUV) photoetching (for example, 193 nano-photoetchings) Long much shorter.Extreme ultraviolet photolithographic uses the mask towards extreme ultraviolet radiation of object (such as silicon wafer) reflection from radiation source (or mask (reticle)), so as to which the pattern from the mask is transferred into the object.The surface of extreme ultraviolet mask On any shortcoming (and the shortcomings that in embedded pole ultraviolet mask) can be caused on the object be imaged shortcoming.Therefore, exist It is important that extreme ultraviolet mask surface is protected during photoetching process.

From traditionally protecting the mask used in the deep-UV lithography of mask surface different using film, currently it is difficult to big Manufacture to scale the effective film for extreme ultraviolet mask.One reason is that the wavelength of extreme ultraviolet radiation is very short and conventional thin The barrier film of film will largely absorb the extreme ultraviolet radiation, so that the barrier film will deform after use several times because of overheat, And will also it substantially reduce the extreme ultraviolet energy for reaching the object.Accordingly, it is desirable to improved in these areas.

The content of the invention

Embodiments of the invention provide a kind of forming method of graphene layer.Methods described includes：In the first substrate Depositing first material layer；And the deposited graphite alkene layer on the first material layer.Methods described also includes：In the graphite Deposition of amorphous silicon layers on alkene layer；And the amorphous silicon layer is bound to the second substrate, so as to form component.Methods described is also Including：The component is set to anneal, so as to which the amorphous silicon layer is transformed into silicon oxide layer.Methods described also includes：From described group Part removes first substrate；And from first material layer described in the assembly removal, so as to expose the graphene layer.

Brief description of the drawings

Read in conjunction with the accompanying drawings described further below, each aspect of the present invention may be best understood.It is emphasized that root According to the standard convention in the industry, various features are not necessarily to scale.In fact, for the sake of discussing clearly, can arbitrarily increase Size that is big or reducing various features.

Fig. 1 is the rough schematic view for the etching system that can benefit from each aspect of the present invention.

Fig. 2 is illustrated according to each aspect of the present invention, a kind of side for being produced on the film used in extreme ultraviolet lithography system The flow chart of method.

Fig. 3 A, Fig. 3 B, Fig. 3 C, Fig. 3 D, Fig. 3 E, Fig. 3 F, Fig. 3 G, Fig. 3 H, Fig. 3 I, Fig. 3 J, Fig. 3 K and Fig. 3 L are according to this Some embodiments of invention, sectional view of the equipment during the various production phases.

[explanation of symbol]

100：Extreme ultraviolet lithography system

102：Radiation source

104：Radiation beam

106：Condenser optics device

107：Film assembly

108：Mask

109：Thin-film membrane

110：Mask objective table

111：Film framework

112：Projection optical device

114：Object objective table

116：Object

200：Method

202、204、206、208、210、212、214、216、218、220、222、224：Operation

300：Component

302：First substrate

304：First material layer

304’：Surface

306：Graphene layer

306’：Surface

307：Carbon atom

308：Amorphous silicon layer

310：Second substrate/silicon substrate

312：Silicon oxide layer

314：Carrier

Embodiment

Disclosure below provides many different embodiments or example for the different characteristic that theme is provided for implementation. Part set forth below and the instantiation of arrangement are to simplify present disclosure.Certainly, these instantiations are only example, and not It is intended for limiting.For example, in the following description by fisrt feature be formed at second feature " on " or second feature " on " can The embodiment for being formed directly to contact including wherein fisrt feature and second feature, and may also comprise wherein described fisrt feature It can cause the fisrt feature may not be direct with the second feature formed with supplementary features between the second feature The embodiment of contact.In addition, present disclosure can in various examples repeated reference numbering and/or letter.This repetition is In succinct and clearly purpose, rather than itself represent the relation between the various embodiments discussed and/or configuration.

In addition, for the sake of ease of explanation, may use herein for example " ... under (beneath) ", " ... below (below) ", " (lower) of bottom ", " ... top (above) ", the space relativity term such as " (upper) on top " comes Illustrate an element illustrated in figure or feature and another (other) element or the relation of feature.The space relativity term It is intended to also include the different orientation of device in use or operation in addition to being orientated shown in figure.Equipment can have other orientations (being rotated by 90 ° or in other orientations), and space relativity used herein describes language and equally can correspondingly explained.

Embodiments of the invention relate generally to the equipment for semiconductor fabrication.More specifically, embodiments of the invention It is related to a kind of thin-film membrane (pellicle membrane) used in extreme ultraviolet photolithographic and makes the thin-film membrane Method.According to an embodiment of the invention, new thin-film membrane includes graphene layer, the graphene layer can be single-layer graphene or Multi-layer graphene (including bilayer and more than two layers).Graphene is fundamentally a kind of mono-layer graphite, that is, is arranged in honeycomb (hexagonal) One layer of lattice combines sp²Carbon atom.Graphene possesses the remarkable properties for being suitable for extreme ultraviolet photolithographic.For example, graphene Layer can be produced very thin, such as several nanometers (nm) to tens nanometers.In addition, graphene has been the most strong material since recording, It is stronger than diamond more than 40 times.In addition, graphene can efficiently conduct heat and electricity and be almost transparent.Although there are these Remarkable properties, but not yet largely production is used as extreme ultraviolet thin-film membrane to graphene.Challenge is always to be difficult to not to graphene Cause to extract individual layer or thin graphene on a large scale in the case of damaging (for example, fold and/or rupture).For as extreme ultraviolet Thin-film membrane, graphene layer should be smooth, and have fold as few as possible.Otherwise, the fold not only influences to be photo-etched into Picture and the source for also turning into thin-film membrane deformation.Embodiments of the invention provide one kind and make smooth graphene on a large scale The novel artistic of layer.

For the sake of discussion, embodiments of the invention refer to the layer for including the material using term " material layer ". Consequently, it is possible to the material layer can include other a kind of (a variety of) elements or composition in addition to the certain material.For example, " nickel Layer " refers to the layer for including nickel, although the layer can additionally comprise a kind of other (a variety of) elements.In addition, " silicon substrate " refers to bag Siliceous substrate, although the substrate can additionally comprise one kind (a variety of) element in addition to silicon.

Fig. 1 shows the exemplary extreme ultraviolet lithography system 100 that can benefit from one or more embodiments of the invention.It is extremely purple Outer etching system 100 includes：Radiation source 102, produce radiation beam 104；Condenser optics device 106；Mask 108, positioned at mask On objective table 110；Film assembly 107, it is placed on mask 108 and with the thin-film membrane being arranged on film framework 111 109；Projection optical device 112；And object 116, on object objective table 114.Other configurations mode and including Or omit what project (items) was possible to.In an embodiment of the present invention, extreme ultraviolet lithography system 100 can be stepper Or scanner (stepper).

In the present embodiment, radiation source 102 provides wavelength and is in extreme ultraviolet scope (e.g., from about 1 nanometer to 100 nanometers) Radiation beam 104.In one embodiment, radiation beam 104 has about 13.5 nanometers of wavelength.Condenser optics device 106 includes Through multi-layer coated collector (multilayer coated collector) and multiple grazing incidence mirror (grazing mirror).Condenser optics device 106 to be collected to radiation beam 104 and shaping, and to by radiation beam (for example, pole Ultraviolet light beam) 104 slit provided to mask 108.

Mask 108 (also referred to as photomask or mask) includes the pattern of one or more target IC apparatus. Mask 108 provides patterning Aerial Images (aerial image) to radiation beam 104.Mask 108 is the reflection in the present embodiment Mask, and such as phase shifting mask (phase-shifting mask, PSM) and/or optical proximity correction (optical can be combined Proximity correction, OPC) etc. RET.Film framework 111 is rigid frame.In one embodiment, Film framework 111 is made up of Anodising aluminium alloy.In the present embodiment, thin-film membrane 109 includes graphene layer.Thin-film membrane 109 protect the surface of mask 108 not polluted by external contaminants.It is thin due to different depths of focus (depth of focus, DOF) Film does not interfere with the patterning Aerial Images caused by mask 108 every the impurity on the surface of mould 109.Mask objective table 110 Such as mask 108 is fixed on mask objective table 110 by vacuum, and in the alignment, focusing, tune of extreme ultraviolet lithography system 100 Accurate location and the movement of mask 108 are provided during flat (leveling) and exposing operation.

Projection optical device 112 includes one or more lens and multiple speculums.The lens can have less than 1 Magnifying power, so as to which the patterning Aerial Images of mask 108 to be decreased to the size of object 116.In one embodiment, object 116 include the semiconductor wafer that coated thereon has photoresist (or resist) layer, and the semiconductor wafer is quick to radiation beam 104 Sense.Object 116 is fixed by object objective table 114, object objective table 114 in being aligned of extreme ultraviolet lithography system 100, gather Accurate location and the movement of object 116 are provided during burnt, leveling and exposing operation, to cause the patterning of mask 108 to take photo by plane Image is repeatedly exposed on object 116 (but other photolithography methods can be used).Radiation beam 104 is exposed in object 116 Afterwards, object 116 is moved to other instruments to be processed further.For example, object 116 can be subjected to resist development and Various etching technics are to form target IC apparatus.

Thin-film membrane 109 plays a significant role in extreme ultraviolet lithography system 100, because thin-film membrane 109 reduces imaging Shortcoming and the probable life for extending mask 108.Conventional films barrier film (for example, those used in deep-UV lithography) generally by Nitrocellulose, fluororesin, plastic resin, synthetic quartz glass etc. are made；And usually several microns of thickness.Those thin-film membranes because Extreme ultraviolet radiation is actually not used to extreme ultraviolet photolithographic to its excessive consumption.In the present embodiment, thin-film membrane 109 includes Graphene layer (or graphene film), the graphene layer (or graphene film) are thinner and stronger than traditional deep ultraviolet thin-film membrane. However, it is difficult to extract graphene layer always in the case where not causing graphene layer damage for extreme ultraviolet film.To stone The damages common of black alkene layer is graphene layer is ftractureed and/or is wrinkled during extraction process.Due to its big surface energy and lack Weary plane ductility, therefore the flat graphene film without structural support is unstable for rolling and (bending to cylindrical shape). Embodiments of the invention provide a kind of new and improved technique for making substantial corrugationless and flat graphene layer. The new and improved technique can be used for manufacturing graphene layer in large quantities for extreme ultraviolet film.Certainly, these graphenes Layer using be not limited only to thin-film membrane, extreme ultraviolet or other for the use of.

Fig. 2 is a kind of flow chart for the method 200 for making the film with graphene layer according to each aspect of the present invention. Before method 200, during and after additional operations can be provided, and some operations can be for the additional implementation of methods described Example is replaced, eliminates or is moved about.Method 200 is example, and in addition to person is not clearly enumerated in claim not It is intended to the limitation present invention.

At operation 202, method 200 (Fig. 2) receives the first substrate 302 (Fig. 3 A).In the present embodiment, the first substrate 302 be silicon substrate, i.e., the first substrate 302 is the substrate for including silicon.Silicon can be monocrystalline silicon or polysilicon.In one embodiment, One substrate 302 is silicon wafer, such as eight inch wafers or 12 inch wafers.In another embodiment, the first substrate 302 is silicon A part for chip.In alternative embodiments, the first substrate 302 can include silicon nitride or one or more iii-vs are partly led Body (such as GaAs).In one embodiment, the first substrate 302 can be circular or rectangle according to the size of aimed thin film. In various embodiments, the first substrate 302 can be several microns to hundreds of microns thickness.

At operation 204, method 200 (Fig. 2) depositing first material layer 304 on the first substrate 302, such as in figure 3b It is illustrated.First material layer 304 is also referred to as " graphene substrate ", because first material layer 304 is used in deposited graphite thereon Alkene layer.In the present embodiment, first material layer 304 includes nickel (Ni).Therefore, first material layer 304 is also referred to as nickel dam.At this In embodiment, first material layer (for example, nickel dam) 304 is deposited by sputtering and with 50 nanometers (nm) to 500 Thickness in nanometer range (such as 50 nanometers to 100 nanometers).In another embodiment, first material layer (for example, nickel dam) 304 With about 100 nanometers of thickness.In alternative embodiments, first material layer 304 can include silicon, copper, glass, aluminium, cobalt, iron, steel, Gold, platinum, titanium, molybdenum, gallium, ruthenium, silver, tungsten, iridium or ceramics.In various embodiments, first material layer 304 can be for example, by chemical gas Mutually deposition (chemical vapor deposition, CVD), physical vapour deposition (PVD) (physical vapor deposition, PVD) and any suitable method such as plating deposits.In addition, first material layer 304 includes the material different from the first substrate 302 Material or different compositions.In certain embodiments, extra play can be formed between the first substrate 302 and first material layer 304. For example, silicon oxide layer can be formed between the first substrate (for example, silicon substrate) 302 and first material layer (for example, nickel dam) 304.

In operation 206, method 200 (Fig. 2) deposited graphite alkene layer 306 (Fig. 3 C) on first material layer 304.At this In embodiment, graphene layer 306 includes single-layer graphene or multi-layer graphene (including bilayer or more than two layers).In the present embodiment In, graphene layer 306 is deposited using chemical vapor deposition (CVD).For example, chemical vapor deposition method can relate to four ranks Section.In the first phase, will for example with the suitable flow rate such as such as 10 standard cubic centimeters per minutes (sccm) to 1,000sccm H₂It is introduced into Deng reducing gas in reaction chamber.The reaction chamber can be set to such as from 600 degrees Celsius (DEG C) to 1,000 DEG C Suitable temperature.In second stage, from the block (bulk) of first material layer 304 (for example, nickel) to first material layer 304 Surface carries out carbon segregation (carbon segregation).In the phase III, because the reduction of chamber temp causes carbon occurs Precipitate (carbon precipitation).In fourth stage, graphene layer is served as in the grain boundary of first material layer 304 The active site of 306 growths, while the chamber is cooled.For example, reaction chamber can be with 500 DEG C/min to 5 DEG C/min Speed cools down.Known other method can also be used in art to deposit in graphene layer 306.In the present embodiment, graphite Alkene layer 306 has the thickness in the range of 5 nanometers to 50 nanometers (such as 5 nanometers to 10 nanometers).For example, graphene layer 306 It can deposit to about 5 nanometer thickness.For another example, graphene layer 306 can be deposited to about 20 nanometer thickness.The thickness of graphene layer 306 can basis The wavelength of extreme ultraviolet radiation to be used designs.On the one hand, absorbed for same extreme ultraviolet wavelength, thicker graphene layer Extreme ultraviolet radiation it is more than the extreme ultraviolet radiation that relatively thin graphene layer is absorbed.Therefore, it is desirable to fully thin so that extremely purple Penetrate the maximized graphene layer of efficiency outside.On the other hand, graphene is relatively brittle, thus has compared with many metal materials Relatively low fracture toughness.Therefore, it is desirable to sufficiently thick to avoid the manufacturing process in film, packaging technology and carrying process The graphene layer of period rupture.

At operation 208, method 200 (Fig. 2) sedimentary 308 (Fig. 3 D) on graphene layer 306.Layer 308 is comprising non- Crystal silicon (α-Si), and therefore it is also referred to as amorphous silicon layer 308.In the present embodiment, amorphous silicon layer 308 is to use chemical vapor deposition Product utilizes silane (SiH₄) as precursor gas at a temperature of about 600 degrees Celsius (DEG C) and in the pressure of about 0.1 support to 10 supports Lower deposition.In alternative embodiments, the deposition of amorphous silicon layer 308 can perform at a temperature of between 560 DEG C to 640 DEG C scopes. As then will explaination, amorphous silicon layer 308 will convert to silicon oxide layer, and can turn into the part of thin-film membrane (that is, thin-film membrane can Including both graphene layer 306 and silicon oxide layer), therefore, the thickness of amorphous silicon layer 308 is also according to extreme ultraviolet radiation to be used Wavelength design.In the present embodiment, thickness of the deposition of amorphous silicon layer 308 extremely in 50 nanometers to 150 nanometer ranges. In one embodiment, amorphous silicon layer 308 is about 100 nanometer thickness.

At operation 210, amorphous silicon layer 308 is bound to the second substrate 310 by method 200 (Fig. 2), so as to form component 300 (Fig. 3 E).In the present embodiment, the second substrate 310 includes silicon, i.e. the second substrate 310 is silicon substrate.Silicon substrate 310 can wrap Containing monocrystalline silicon or polysilicon.In one embodiment, silicon substrate 310 is silicon wafer, such as eight inch wafers or 12 inch wafers. In another embodiment, the second substrate 310 is a part for silicon wafer.In alternative embodiments, the second substrate 310 can include nitrogen SiClx or one or more Group III-V semiconductors (such as GaAs).First substrate 302 can have identical with the second substrate 310 Or different shape.In the present embodiment, amorphous silicon layer 308 is combined by Van der Waals force (van der Waals force) To the second substrate 310.

At operation 212, method 200 (Fig. 2) makes component 300 anneal, so as to which amorphous silicon layer 308 is transformed into silicon oxide layer 312 (Fig. 3 F).In the present embodiment, component 300 is at a temperature in the range of 600 DEG C to 1,000 DEG C and with oxygen Annealed in surrounding environment.Amorphous silicon layer 308 is transformed into by the annealing process mainly includes silica (SiO₂) layer 312.Layer 312 are also referred to as silicon oxide layer 312.In addition, the annealing process strengthens the knot between the second substrate 310 and silicon oxide layer 312 Closing, this is beneficial to subsequent technique, such as to the first substrate 302 and the technique of the execution of first material layer (for example, nickel dam) 304.

At operation 214, method 200 (Fig. 2) removes the first substrate 302 from component 300.In one embodiment, 214 are operated Including grinding technics or (chemical mechanical polishing, CMP) technique is chemically-mechanicapolish polished, followed by it is a kind of Or a variety of etching technics.To promote this embodiment, grinding technics or CMP process partly remove the first substrate 302 Until the thin layer of only the first substrate 302 is remained in component 300.For example, the remainder layer of the first substrate 302 can be To 50 angstroms of thickness.This prevents grinding technics or CMP process from inadvertently removing first material layer 304 and damage graphene Layer 306.In one embodiment, operation 214 determines when to stop above grinding technics or chemically mechanical polishing using timer Technique.After grinding technics or CMP process, operation 214 removes its of the first substrate 302 using etching technics Remaining layer, the etching technics can be wet etching or dry etching.Etching technics has selectively to the first substrate 302, and Stop at first material layer 304.For example, wet etching process may include to perform etching in following item：Through dilute hydrofluoric acid (diluted hydrofluoric acid, DHF)；Potassium hydroxide (potassium hydroxide, KOH) solution；Ammonia；Contain Hydrofluoric acid (HF), nitric acid (HNO₃) and/or acetic acid (CH₃COOH solution)；Or other suitable wet etching agent.For example, dry type Etching technics can implementation oxygen-containing gas, fluoro-gas (for example, CF₄、SF₆、CH₂F₂、CHF₃And/or C₂F₆), chlorine-containing gas (example Such as, Cl₂、CHCl₃、CCl₄And/or BCl₃), bromine-containing gas are (for example, HBr and/or CHBR₃), gas containing iodine, other suitable gas And/or plasma and or its combination.In one embodiment, the first substrate 302 includes silicon and first material layer 304 includes nickel, Potassium hydroxide (KOH) solution can be used optionally to be etched as wet etching agent, the wet etching agent for the etching technics Silicon rather than nickel.In another embodiment, etching technics can use fluoro-gas (for example, CF in dry etch process₄、SF₆、 CH₂F₂、CHF₃And/or C₂F₆).The fluoro-gas optionally etches silicon rather than nickel.

In another embodiment, operation 214 (that is, without using grinding technics, is chemically-mechanicapolish polished using dry etch process Technique or wet etching process) remove whole first substrate 302.Dry etch process has selectivity to the first substrate 302, And stop at first material layer 304.Etching gas can be one or more of above-mentioned gas.In one embodiment, first Substrate 302 includes silicon and first material layer 304 includes nickel, and fluoro-gas can be used (for example, CF in dry etch process₄、SF₆、 CH₂F₂、CHF₃And/or C₂F₆) come optionally remove the first substrate (for example, silicon substrate) 302 and first material layer (for example, Nickel dam) stop at 304.In another embodiment, wet etching process can be used with using in above-mentioned wet etching agent in operation 214 One of or more persons remove whole first substrate 302.In one of for example above-mentioned embodiment of use example first is removed from component 300 After substrate 302, the surface 304 ' of first material layer 304 is exposed, as shown in Fig. 3 G.

At operation 216, method 200 (Fig. 2) removes first material layer 304 from component 300.In one embodiment, moving Before first material layer 304, the surface 304 ' that is exposed of 216 pairs of first material layers 304 of operation is cleaned.This for example, by Technique removes any residue before grinding, polishing and/or etching to the first substrate 302 etc..Then, operation 216 uses one Kind or a variety of etching technics remove first material layer 304.In one embodiment, first material layer 304 includes nickel (therefore it is " nickel dam 304 ", and 216 are operated by the way that component 300 is immersed into chloride containing iron (FeCl₃) wet etching agent in remove the first material The bed of material (for example, nickel dam) 304.In another embodiment, operation 216 uses dry etch process and is used as quarter by the use of chlorine-containing gas Gas is lost to remove first material layer (for example, nickel dam) 304.For example, the dry etch process can supply chlorine and oxygen extremely Wherein it is placed with the etching cavity of component 300, and produces the inductive for etching away first material layer (for example, nickel dam) 304 Plasma.For another example, the dry etch process can supply boron chloride (BCl₃) gas and argon gas be to being wherein placed with component In 300 etching cavity and generation etches away the inductively coupled plasma of first material layer (for example, nickel dam) 304.From group After part 300 removes first material layer 304, the surface 306 ' of graphene layer 306 is exposed, as shown in Fig. 3 H.

At operation 218, method 200 (Fig. 2) is cleaned or handled to improve graphene layer to the surface 306 ' that is exposed 306 quality.When depositing graphene layer 306 to first material layer 304 at operation 206, some carbon atoms 307 can expand It is dissipated in the grain boundary of first material layer 304, as shown in Fig. 3 I.Therefore, surface 306 ' can remove first material layer Carbon residue is included after 304.Operation 218 applies oxygen plasma to the surface 306 ' of graphene layer 306.Oxygen plasma Removing carbon residue (if present) simultaneously smooths out surface 306 ', so as to improve the purity of graphene layer 306 and flat Degree.

At operation 220, component 300 is attached to carrier 314 (Fig. 3 J) by method 200 (Fig. 2).In one embodiment, stone Black alkene layer 306, more specifically, the directly contact carrier 314 of surface 306 '.In one embodiment, carrier 314 is that adhesive-free carries Body, and electrostatic charge is used as the mechanism for adhering to.For example, carrier 314 can be made up of ceramics and by quiet for producing The one or more battery power supply of electric charge.In addition, carrier 314 can only along carrier 314 periphery (for example, the side of carrier 314 Edge) it is attached to graphene layer 306.For example, carrier 314 can be in cup (for example, suction cup) shape, and when component 300 is attached to carrier When 314, the edge of only described cup directly contacts graphene layer 306.In one embodiment, the edge of carrier 314 conforms to film Shape, to cause graphene layer 306 to be flattened in subsequent manufacturing procedures.It has an advantage that it can using one of carrier 314 Graphene layer 306 is attached to easily and is separated from graphene layer 306 and will not be damaged graphene layer 306.

At operation 222, method 200 (Fig. 2) removes the second substrate 310 from component 300.In one embodiment, 222 are operated The second substrate 310 is removed using dry etch process.For example, the dry etch process can implementation oxygen-containing gas, containing fluorine gas Body is (for example, CF₄、SF₆、CH₂F₂、CHF₃And/or C₂F₆), chlorine-containing gas is (for example, Cl₂、CHCl₃、CCl₄And/or BCl₃), it is brominated Gas is (for example, HBr and/or CHBR₃), gas containing iodine, other suitable gas and/or plasma and or its combination.In addition, institute Dry etch process is stated to be controlled so as to remove the second substrate while keeping silicon oxide layer 312 to be located on graphene layer 306 310 (Fig. 3 K).In another embodiment, operation 222 uses grinding technics or chemically mechanical polishing (CMP) technique followed by one kind Or a variety of etching technics remove the second substrate 310.To promote this embodiment, operation 222 can control grinding using timer Technique or CMP process, to cause grinding technics or CMP process inadvertently not to remove silicon oxide layer 312。

Reference picture 3K, there is shown with the component 300 for being attached to carrier 314.Component 300 includes graphene layer 306 and placement Silicon oxide layer 312 on graphene layer 306.In one embodiment, method 200 can also for example by dry etch process come Silicon oxide layer 312 is removed, and only leaves the graphene layer 306 that carrier 314 is attached to stretching mode.To promote this embodiment, Film framework (for example, film framework 111 in Fig. 1) can be then attached to graphene layer 306 by method 200, then from graphite The carrier of separating 314 (operation 224) of alkene layer 306.

At operation 224, method 200 (Fig. 2) removes carrier 314, so as to produce component 300, as shown in Fig. 3 L.Group Part 300 has the graphene layer 306 and silica to be worked together as thin-film membrane (such as thin-film membrane 109 in Fig. 1) Layer 312.For example, film framework (such as film framework 111) can be attached to component 300 to make film assembly 107 (Fig. 1). Film framework can mount to graphene layer 306 or be attached to silicon oxide layer 312.When film framework is attached to graphene layer 306, Silicon oxide layer 312 turns into the outer layer of thin-film membrane, and graphene layer 306 turns into the internal layer of thin-film membrane.In another embodiment When film framework is attached to silicon oxide layer 312, graphene layer 306 turns into the outer layer of thin-film membrane, and silicon oxide layer 312 turns into The internal layer of thin-film membrane.

In process above, graphene layer 306 is always by least one film or equipment (such as first material layer 304, amorphous Silicon layer 308, silicon oxide layer 312 and carrier 314) support.Therefore, graphene layer 306 is always stretched, and its shape is through described Technique keeps substantially the same.Therefore, 306 substantial corrugationless of graphene layer and rupture.In addition, embodiments of the invention use Various dry etch process, this advantageously makes graphene layer 306 maintain corrugationless and rupture.Further, implementation of the invention Example can implementation be used to using graphene largely produce film or thin-film membrane.It is non-that these are that embodiments of the invention are provided Restricted benefit.

In an illustrative aspect, embodiments of the invention are related to a kind of forming method of graphene layer.Methods described Including：In the first substrate depositing first material layer；And the deposited graphite alkene layer on the first material layer.The side Method also includes：The deposition of amorphous silicon layers on the graphene layer；And the amorphous silicon layer is bound to the second substrate, so as to Form component.Methods described also includes：The component is set to anneal, so as to which the amorphous silicon layer is transformed into silicon oxide layer.It is described Method also includes：From the first substrate described in the assembly removal；And from first material layer described in the assembly removal, so as to sudden and violent Expose the graphene layer.

Described method also includes：The component is attached to carrier, wherein the graphene layer directly contacts the load Body；And it is described the component is attached to the carrier after, from the second substrate described in the assembly removal.

In the described method, each of first substrate and second substrate include silicon, and described One material layer includes nickel.

In the described method, removal first substrate includes dry etch process.

In the described method, the removal first material layer includes dry etch process.

In the described method, after the removal first material layer, in addition to：By oxygen plasma apply to The surface relative with another surface of the graphene layer of the graphene layer, another surface of the graphene layer with The silicon oxide layer interfaces with.

In the described method, removal second substrate includes dry etch process.

In the described method, the graphene layer has between 5 nanometers of thickness to 50 nanometer ranges, and the amorphous Silicon layer has between 50 nanometers of thickness to 150 nanometer ranges.

In the described method, it is described to make the component annealing be in the temperature in the range of 600 degrees Celsius to 1000 DEG C Degree is lower and is performed in the surrounding environment with oxygen.

In the described method, the amorphous silicon layer is to be bound to second substrate by Van der Waals force.

In in terms of the another exemplary, embodiments of the invention are related to a kind of forming method of graphene layer.Methods described Including：The deposited nickel layer on the first silicon substrate；And the deposited graphite alkene layer on the nickel dam.Methods described also includes： The deposition of amorphous silicon layers on the graphene layer；And the amorphous silicon layer is bound to by the second silicon by Van der Waals force and served as a contrast Bottom, so as to form component.Methods described also includes：The component is set to anneal in the surrounding environment with oxygen, so as to by described in Amorphous silicon layer is transformed into silicon oxide layer.Methods described also includes：From the first silicon substrate described in the assembly removal；From the component Remove the nickel dam；The component is attached to carrier, wherein the graphene layer directly contacts the carrier；And described The component is attached to the carrier afterwards from the second silicon substrate described in the assembly removal.

In the described method, it is described remove first silicon substrate and it is described remove it is each in second silicon substrate Person includes dry etch process.

In the described method, the component is attached to the carrier after the removal nickel dam and described Before, in addition to：Oxygen plasma is applied to the table relative with another surface of the graphene layer of the graphene layer Face, another surface and the silicon oxide layer of the graphene layer interface with.

In the described method, removal first silicon substrate includes CMP process.

In the described method, the component is to be attached to the carrier by electrostatic charge.

In another illustrative aspect, this disclosure relates to a kind of forming method of graphene layer.Methods described includes： One substrate deposited nickel layer；And the deposited graphite alkene layer on the nickel dam.Methods described also includes：In the graphene Deposition of amorphous silicon layers on layer；And the amorphous silicon layer is bound to the second substrate, so as to form first assembly.Methods described Also include：The amorphous silicon layer is transformed into silicon oxide layer in the first assembly；Described the is removed from the first assembly One substrate and the nickel dam；And carrier is attached to the graphene layer, so as to form the second component.Methods described is also wrapped Include：From the second substrate described in second assembly removal.

In the described method, the removal first substrate and the nickel dam include dry etch process, and described Removing second substrate includes another dry etch process.

In the described method, the deposition nickel dam is carried out by sputtering, and the nickel dam has between 50 Nanometer to 500 nanometer ranges thickness.

In the described method, the graphene layer has between 5 nanometers of thickness to 50 nanometer ranges, and the amorphous Silicon layer has between 50 nanometers of thickness to 150 nanometer ranges.

In the described method, after the removal first substrate and the nickel dam, in addition to：By oxygen plasma Body applies to the surface of the graphene layer.

Foregoing has outlined the feature of some embodiments, so that those of ordinary skill in the art are better understood this hair Bright each side.Those of ordinary skill in the art are, it should be understood that they can easily use the present invention as design or change it The basis of his technique and structure is to implement and embodiment identical purpose described herein and/or realize with being situated between herein The advantages of embodiment to continue is identical.Those of ordinary skill in the art will also be recognized that these equivalent constructions without departing from this hair Bright spirit and scope, and they can to it, various changes can be made, generation under conditions of without departing substantially from spirit and scope of the present invention Replace and change.

Claims (1)

1. A kind of 1. forming method of graphene layer, it is characterised in that including：

   In the first substrate depositing first material layer；

   The deposited graphite alkene layer on the first material layer；

   The deposition of amorphous silicon layers on the graphene layer；

   The amorphous silicon layer is bound to the second substrate, so as to form component；

   The component is set to anneal, so as to which the amorphous silicon layer is transformed into silicon oxide layer；

   From the first substrate described in the assembly removal；And

   From first material layer described in the assembly removal, so as to expose the graphene layer.