(19)
(11)EP 3 648 146 A1

(12)EUROPEAN PATENT APPLICATION

(43)Date of publication:
06.05.2020 Bulletin 2020/19

(21)Application number: 18204338.0

(22)Date of filing:  05.11.2018
(51)Int. Cl.: 
H01L 21/02  (2006.01)
H01L 21/311  (2006.01)
(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR
Designated Extension States:
BA ME
Designated Validation States:
KH MA MD TN

(71)Applicant: IMEC vzw
3001 Leuven (BE)

(72)Inventors:
  • CHAN, Boon Teik
    3001 Leuven (BE)
  • DE MARNEFFE, Jean-Francois
    3001 Leuven (BE)
  • MARINOV, Daniil
    3001 Leuven (BE)
  • LIN, Han Chung
    3001 Leuven (BE)
  • ASSELBERGHS, Inge
    3001 Leuven (BE)

(74)Representative: DenK iP 
Leuvensesteenweg 203
3190 Boortmeerbeek
3190 Boortmeerbeek (BE)

  


(54)REMOVING AN ORGANIC SACRIFICIAL MATERIAL FROM A 2D MATERIAL


(57) In a first aspect, the present invention relates to a method for removing an organic sacrificial material (301) from a 2D material (200), comprising: (a) providing a target substrate (120) having thereon the 2D material (200) and a layer of the organic sacrificial material (301) over the 2D material (200), (b) infiltrating the organic sacrificial material (301) with a metal or ceramic material (311), and (c) removing the organic sacrificial material (301).




Description

Technical field of the invention



[0001] The present invention relates to the provision of two-dimensional (2D) materials and in particular to the provision of 2D materials in semiconductor devices.

Background of the invention



[0002] In view of seeking to uphold Moore's law and the associated continuous quest for scaling down, there is a growing interest in the field of semiconductor devices to make use of 2D materials such as graphene, transition metal dichalcogenides (MX2), hexagonal boron nitride (h-BN), etc. by integrating them in these semiconductor devices.

[0003] One promising way to achieve this integration is to grow, e.g. via chemical vapour deposition (CVD), the 2D material on a host substrate and then transfer the 2D material to a target substrate (e.g. a semiconductor substrate). An example of this approach was disclosed by McCreary et al. (2016) (MCCREARY, Kathleen M., et al. The effect of preparation conditions on Raman and photoluminescence of monolayer WS 2. Scientific reports, 2016, 6: 35154.). Therein, after CVD growing a WS2 2D layer on a Si/SiO2 host substrate (therein referred to as a 'growth substrate'), a thin layer of polymethyl methacrylate (PMMA) was spun onto the surface of the entire growth substrate then submerged in buffered oxide etchant. After several hours, the oxide layer was removed, freeing the WS2/PMMA film from the growth substrate. The sample was subsequently transferred to H2O to rinse chemical etchants, where a fresh Si/SiO2 substrate is used to lift the film out of the water. A 2000 rpm spin and 150 °C bake improved the uniformity and adhesion to the substrate, after which the PMMA was dissolved in acetone.

[0004] However, a disadvantage of methods like the above is that the organic sacrificial material, e.g. PMMA, is only partially removed from the 2D material; a residue of the organic sacrificial material remains on the 2D material. As such, there is still a need in the art for better methods to transfer a 2D material to a target substrate and subsequently remove the organic sacrificial material.

Summary of the invention



[0005] It is an object of the present invention to provide good methods for removing an organic sacrificial material from a 2D material. It is a further object of the present invention to provide good structures associated with said method. This objective is accomplished by a method and structure according to the present invention.

[0006] It is an advantage of embodiments of the present invention that the top surface of the 2D material can be completely uncovered (e.g. freed from any organic sacrificial material).

[0007] It is an advantage of embodiments of the present invention that the organic sacrificial material can be removed without damaging the 2D material.

[0008] It is an advantage of embodiments of the present invention that a metal or ceramic material can act as a protection and/or passivation layer for the 2D material.

[0009] It is an advantage of embodiments of the present invention that the method is compatible with a variety of 2D materials.

[0010] It is an advantage of embodiments of the present invention that the 2D materials can be used in various functions in practical devices (e.g. in semiconductor devices).

[0011] It is an advantage of embodiments of the present invention that the good transfer of 2D materials is facilitated, thereby allowing them to be more easily integrated into different applications.

[0012] It is an advantage of embodiments of the present invention that the method is relatively straightforward in its execution and is economical.

[0013] It is an advantage of embodiments of the present invention that a dielectric layer can be formed on the 2D material by using the metal or ceramic material as a seed layer.

[0014] It is an advantage of embodiments of the present invention that a dielectric layer can be formed from the metal or ceramic material as such.

[0015] It is an advantage of embodiments of the present invention that a portion of the organic sacrificial material may be made to be irreversibly physically adsorbed to the 2D material.

[0016] It is an advantage of embodiments of the present invention that the method is compatible with a variety of substrates, including structured substrates.

[0017] It is an advantage of embodiments of the present invention that a conformal 2D material, a conformal organic sacrificial material (e.g. the irreversibly physically adsorbed portion thereof) and/or a conformal dielectric layer can be provided, even on a structured substrate.

[0018] In a first aspect, the present invention relates to a method for removing an organic sacrificial material from a 2D material, comprising: (a) providing a target substrate having thereon the 2D material and a layer of the organic sacrificial material over the 2D material, (b) infiltrating the organic sacrificial material with a metal or ceramic material, and (c) removing the organic sacrificial material.

[0019] In a second aspect, the present invention relates to a structure, comprising: (i) a target substrate, (ii) a 2D material on the target substrate, and (iii) a layer over (and typically on) the 2D material, the layer comprising an organic sacrificial material, the organic sacrificial material comprising a metal or ceramic material.

[0020] Particular and preferred aspects of the invention are set out in the accompanying independent and dependent claims. Features from the dependent claims may be combined with features of the independent claims and with features of other dependent claims as appropriate and not merely as explicitly set out in the claims.

[0021] Although there has been constant improvement, change and evolution of devices in this field, the present concepts are believed to represent substantial new and novel improvements, including departures from prior practices, resulting in the provision of more efficient, stable and reliable devices of this nature.

[0022] The above and other characteristics, features and advantages of the present invention will become apparent from the following detailed description, taken in conjunction with the accompanying drawings, which illustrate, by way of example, the principles of the invention. This description is given for the sake of example only, without limiting the scope of the invention. The reference figures quoted below refer to the attached drawings.

Brief description of the drawings



[0023] Fig. 1 to 17 schematically show vertical cross-sections of structures in exemplary methods according to the present invention.

[0024] In the different figures, the same reference signs refer to the same or analogous elements.

Description of illustrative embodiments



[0025] The present invention will be described with respect to particular embodiments and with reference to certain drawings but the invention is not limited thereto but only by the claims. The drawings described are only schematic and are non-limiting. In the drawings, the size of some of the elements may be exaggerated and not drawn on scale for illustrative purposes. The dimensions and the relative dimensions do not correspond to actual reductions to practice of the invention.

[0026] Furthermore, the terms first, second, third and the like in the description and in the claims, are used for distinguishing between similar elements and not necessarily for describing a sequence, either temporally, spatially, in ranking or in any other manner. It is to be understood that the terms so used are interchangeable under appropriate circumstances and that the embodiments of the invention described herein are capable of operation in other sequences than described or illustrated herein.

[0027] Moreover, the terms top, over, under and the like in the description and the claims are used for descriptive purposes and not necessarily for describing relative positions. It is to be understood that the terms so used are interchangeable with their antonyms under appropriate circumstances and that the embodiments of the invention described herein are capable of operation in other orientations than described or illustrated herein.

[0028] It is to be noticed that the term "comprising", used in the claims, should not be interpreted as being restricted to the means listed thereafter; it does not exclude other elements or steps. It is thus to be interpreted as specifying the presence of the stated features, integers, steps or components as referred to, but does not preclude the presence or addition of one or more other features, integers, steps or components, or groups thereof. The term "comprising" therefore covers the situation where only the stated features are present and the situation where these features and one or more other features are present. Thus, the scope of the expression "a device comprising means A and B" should not be interpreted as being limited to devices consisting only of components A and B. It means that with respect to the present invention, the only relevant components of the device are A and B.

[0029] Reference throughout this specification to "one embodiment" or "an embodiment" means that a particular feature, structure or characteristic described in connection with the embodiment is included in at least one embodiment of the present invention. Thus, appearances of the phrases "in one embodiment" or "in an embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment, but may. Furthermore, the particular features, structures or characteristics may be combined in any suitable manner, as would be apparent to one of ordinary skill in the art from this disclosure, in one or more embodiments.

[0030] Similarly, it should be appreciated that in the description of exemplary embodiments of the invention, various features of the invention are sometimes grouped together in a single embodiment, figure, or description thereof for the purpose of streamlining the disclosure and aiding in the understanding of one or more of the various inventive aspects. This method of disclosure, however, is not to be interpreted as reflecting an intention that the claimed invention requires more features than are expressly recited in each claim. Rather, as the following claims reflect, inventive aspects lie in less than all features of a single foregoing disclosed embodiment. Thus, the claims following the detailed description are hereby expressly incorporated into this detailed description, with each claim standing on its own as a separate embodiment of this invention.

[0031] Furthermore, while some embodiments described herein include some but not other features included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the invention, and form different embodiments, as would be understood by those in the art. For example, in the following claims, any of the claimed embodiments can be used in any combination.

[0032] In the description provided herein, numerous specific details are set forth. However, it is understood that embodiments of the invention may be practiced without these specific details. In other instances, well-known methods, structures, and techniques have not been shown in detail in order not to obscure an understanding of this description.

[0033] Reference will be made to transistors. These are devices having a first main electrode such as a drain, a second main electrode such as a source and a control electrode such as a gate for controlling the flow of electrical charges between the first and second main electrodes.

[0034] The following term is provided solely to aid in the understanding of the invention.

[0035] As used herein, and unless otherwise specified, a 2D (two-dimensional) - material is a crystalline material consisting of a single atomically thin layer of covalently bonded atoms or consisting of several (e.g. 2 or 3) such layers held together by van der Walls forces. Self-assembled monolayers (SAMs) are not 2D materials in the sense of the present invention since they are not crystalline and they are not consisting of an atomically thin layer but are consisting of a thicker layer which thickness is the length of the molecule self-assembling in the SAM. Preferred 2D materials in the sense of the present invention are mineral materials.

[0036] As used herein the term "metal or ceramic material precursor" relates to a precursor in the formation of a metal or of a ceramic material. In the present invention, preferred types of "metal or ceramic material precursor" are precursors to metal oxides or to metalloid oxides.

[0037] In a first aspect, the present invention relates to a method for removing an organic sacrificial material from a 2D material, comprising: (a) providing a target substrate having thereon the 2D material and a layer of the organic sacrificial material over the 2D material, (b) infiltrating the organic sacrificial material with a metal or ceramic material, and (c) removing the organic sacrificial material.

[0038] Although the target substrate may be of any nature, in preferred embodiments, the target substrate is a semiconductor substrate. In embodiments, the semiconductor substrate may be a Si substrate, a Ge substrate, a semiconductor-on-insulator substrate (SOI; e.g. Si-on-insulator or Ge-on-insulator) or a III-V substrate. In embodiments, the target substrate may be a structured substrate.

[0039] As used herein, and unless provided otherwise, a structured substrate (or a patterned substrate) is a substrate having a top surface comprising valleys and peaks, as opposed to having a planar top surface. For instance, the valleys may be at least 1 nm deep and the peaks may be at least one nm high. As another example, the valleys may be at least 10 nm deep and the peaks may be at least 10 nm high. These are merely examples and the present invention is compatible with any substrate top surface morphology. In embodiments, the 2D material may be a 2D conductor, a 2D semiconductor or a 2D dielectric. In embodiments, the 2D material may be for use in a semiconductor device (e.g. a transistor). In embodiments, the 2D material may be forming a channel layer, a source or drain electrode, a gate dielectric, or a gate electrode.

[0040] The present invention is applicable to any type of 2D material since the steps of the method are performed on the overlying organic sacrificial material and since the 2D material is protected by the method. In embodiments, the 2D material may be selected from X-enes (2D materials made of a single element, e.g. graphene, germanene, silicene, phosphorene, borophene, stanine, bismuthene), transition metal dichalcogenides (also called TMDs, they are of the form MX2 where M is a transition metal and X is a chalcogen, e.g. MoS2, WS2), semimetal chalcogenides (also called SMCs, they are of the form M2X2 where M is a semimetal (e.g. Ga or In) and X is a chalcogen (e.g. S or Se), MX-enes (2D materials of the form Mn+1Xn wherein n is 1, 2, or 3, where M is one or more transition metals, and X is carbon or nitrogen, e.g. transition metal carbide, nitride or carbonitride, such as Ti2C, (Ti0.5,Nb0.5)2C, V2C, Nb2C, MO2C, Ti3C2 , Ti3CN, Zr3C2, Hf3C2, Mo2TiC2, and Cr2TiC2), hexagonal boron nitride (h-BN), graphene oxide, Si2BN, borocarbonitrides, and germanane, amongst others.

[0041] The present invention is particularly useful when applied to TMDs which are a promising class of materials to form transistor channels and for which damages to the 2D material, or the presence of organic residues, after removal of a sacrificial organic material have been reported.

[0042] In preferred embodiments, the 2D material may be conformal with the target substrate thereunder. For example, the target substrate may be a structured substrate and the 2D material may follow valleys and peaks thereof.

[0043] In embodiments, the organic sacrificial material may be a polymer. In embodiments, the polymer may comprise functional groups suitable for coordinating with the first precursor (cf. infra). In embodiments, the polymer may be an electron donor, or may comprise an electron donor group, for coordinating with a Lewis acid. In embodiments, the polymer may comprise one or more heteroatoms (e.g. oxygen or nitrogen), such as in a carbonyl, ester, amide or amine functionality. In embodiments, the polymer may be poly(methyl methacrylate) (PMMA), polyphthalaldehyde, or polyphthalamide.

[0044] In embodiments, the organic sacrificial material may be conformal with the 2D material thereunder.

[0045] In embodiments, the metal material may be W. In embodiments, the ceramic material may be a metal oxide or metalloid oxide, such as Al2O3, ZnO, TiO2, SiO2 or HfO2.

[0046] In embodiments, step a may comprise: (a1) providing a host substrate having thereon the 2D material, (a2) covering the 2D material with a layer of organic sacrificial material, and (a3) transferring the 2D material and the layer of organic sacrificial material onto the target substrate (in such a way that the 2D material comes in mechanical contact with the target substrate). In embodiments, the host substrate may be a sapphire substrate, a Si substrate or a SOI (e.g. Si on SiO2) substrate. In embodiments, step a2 may comprise spin coating the organic sacrificial material over the 2D material. In embodiments, step a3 may comprise bonding a thermal tape to the layer of organic sacrificial material and transferring the stack of the 2D material, the layer of organic sacrificial material and the thermal tape onto the target substrate (in such a way that the 2D material comes in mechanical contact with the target substrate).

[0047] In embodiments, at least a lower portion of the organic sacrificial material in step a (e.g. in step a2) may be irreversibly physically adsorbed to the 2D material. By irreversibly physically adsorbed, it is meant that the potion cannot be removed by any solvent. For instance, it survives contact with benzene for 3 hours.

[0048] In embodiments, the lower portion may have a thickness of from 1 to 10 nm, preferably from 1 to 4 nm. In embodiments, the lower portion of the layer of organic sacrificial material irreversibly physically adsorbed to the 2D material may be formed by a step of baking the layer of organic sacrificial material at a temperature above its glass transition temperature Tg (but low enough to avoid calcination). In embodiments, the step of baking the layer of organic sacrificial material may be performed for between 6 and 24 hours, preferably between 12 and 24 hours. Preferably, the baking step is followed by a step of removing non-irreversibly physically adsorbed organic sacrificial material. This can be performed by exposing the organic sacrificial material to a solvent for at least 30 min, preferably at least 1h, more preferably at least 2h, and most preferably at least 3h. An appropriate solvent is a solvent capable of dissolving the organic sacrificial material in bulk form. For instance, if the organic sacrificial material is PMMA, appropriate solvents are benzene, toluene, and xylene amongst others.

[0049] In embodiments, forming an irreversibly physically adsorbed organic sacrificial material on a 2D material on a structured substrate may comprise 1) providing the structured substrate, 2) providing the 2D material conformally on the structured substrate, 3) providing an organic sacrificial material in such a way that it planarizes the valleys and peaks of the structured substrate, so as to obtain a layer of organic sacrificial material having a planar top surface, 4) baking the layer of organic sacrificial material at a temperature above its glass transition temperature Tg (but low enough to avoid calcination), and 5) removing non-irreversibly physically adsorbed organic sacrificial material. Preferably, step 5) removes any non-irreversibly physically adsorbed organic sacrificial material. Step 5) may typically be performed by exposing the organic sacrificial material to a solvent as explained above.

[0050] In embodiments, step b may comprise a sequential infiltration synthesis (SIS). SIS may preferentially be performed at a temperature of from 10 °C to 110 °C, preferably from 20 ºC to 90 ºC. In embodiments, step b may comprise: (b1) exposing the organic sacrificial material to a first precursor, and (b2) exposing the organic sacrificial material to a second precursor.

[0051] Steps (b1) and (b2) results in the infiltration of the organic sacrificial material with a metal or ceramic material. It can advantageously comprise exposing the organic sacrificial material to a first metal or ceramic material precursor, thereby typically absorbing the first metal or ceramic material precursor in the organic sacrificial material, and subsequently exposing the organic sacrificial material to a second metal or ceramic material precursor, thereby typically chemically reacting both precursors to form the metal or ceramic material. The first and second metal or ceramic material precursors are typically reagents in the formation of the metal or ceramic material and are not typically metals or ceramic materials themselves. In preferred embodiments, the first and/or second metal or ceramic material precursors may be in a gaseous phase. In yet more preferred embodiments, both the first and second metal or ceramic material precursors may be in a gaseous phase.

[0052] In general, for the first precursor, any CVD/ALD precursors of metal or ceramic material which can infiltrate the organic sacrificial material may be used. Preferably, the first precursor reacts with the second precursor at a temperature from 10 °C to 110 °C, preferably from 20 ºC to 90 ºC. Typically, the first precursor is able to infiltrate the organic sacrificial material. The infiltrated metal or ceramic material can advantageously be obtained through a reduction (typically for the metal) or oxidation (typically for the ceramic) of the first metal or ceramic material precursor by means of the second metal or ceramic material precursor (here typically a reductant or oxidant). In embodiments, the first precursor may be a Lewis acidic metal or metalloid compound. In embodiments, the Lewis acidic metal or metalloid compound may be selected from Al(CH3)3 (trimethylaluminum, TMA), Zn(C2H5)2, TiCl4, SiCl4, HfCl4 and WF6. In embodiments, the second precursor may be a reductant (e.g. for the first precursor) or an oxidant (e.g. for the first precursor). In embodiments, the reductant may be SiH4, SiH2, or H2. In embodiments, the oxidant may be H2O or O3. In embodiments, to infiltrate a metal in the organic sacrificial material, the first precursor may be WF6 and the second precursor may be a reductant (e.g. SiH4, SiH2, or H2). In embodiments, to infiltrate a ceramic material in the organic sacrificial material, the first precursor may be a Lewis acidic metal or metalloid selected from Al(CH3)3, Zn(C2H5)2, TiCl4, SiCl4, HfCl4 and the second precursor may be an oxidant (e.g. H2O or O3). In embodiments, step b may be performed in a reaction chamber. In preferred embodiments, step b1 may further comprise, after exposing the organic sacrificial material to the first precursor, purging the reaction chamber with an inert gas (e.g. N2). In preferred embodiments, step b2 may further comprise, after exposing the organic sacrificial material to the second precursor, purging the reaction chamber with an inert gas (e.g. N2).

[0053] In embodiments, a sequence comprising step b1 and step b2 may be performed from 1 to 100 times, preferably from 2 to 20 times, yet more preferably from 3 to 10 times.

[0054] The result of step b is a metal or ceramic material-infiltrated organic sacrificial material. This resulting material typically comprises an organic part in which a ceramic or metallic material is embedded. Most typically, chains of the organic sacrificial material are ruptured during the infiltration process, leading to the formation of a mixture of 1) organic units, smaller than the original organic sacrificial material, and 2) ceramic or metal material. The result of step b can also typically be seen as a ceramic or metal material matrix in which organic units, smaller than the original organic sacrificial material, are dispersed.

[0055] In embodiments, step c may comprise a thermal treatment, a plasma treatment, or a combination thereof. These treatments are preferably performed in an inert atmosphere. In embodiments, the thermal treatment and/or the plasma treatment may be combined with a UV treatment. This is advantageous as it permits a faster treatment, at a lower temperature, and with less risk of damage to the 2D material. In embodiments, the thermal treatment may comprise heating the organic sacrificial material to a temperature sufficient to achieve thermal decomposition of the organic sacrificial material (in the given conditions, e.g. in presence of a UV and/or plasma treatment, or e.g. in absence of both UV and plasma treatment). Typically, a temperature of 400°C or more, or of 500°C or more is sufficient for most organic sacrificial materials. In the case of the organic sacrificial material being PMMA, a temperature of 400°C or above can for instance be used. When a combination of a thermal treatment and a UV treatment is used, lower decomposition temperatures can be achieved. For instance, a temperature in the range 300-400°C may suffice. In embodiments, the plasma treatment is preferably an indirect plasma treatment such as a downstream or remote plasma treatment (a plasma processing method in which the interaction between the plasma and the material occurs at a location remote from the plasma in the plasma afterglow). This is advantageous as it is less prone to damage the 2D material. The plasma treatment may, for instance, comprise an H2 (remote) or H2/N2 plasma treatment.

[0056] When a plasma treatment is used, it is preferably used together with a UV treatment. Most preferably, when a plasma treatment is used, it is an indirect plasma treatment (e.g. a downstream plasma treatment such as an H2 downstream plasma treatment). Even more preferably, when a plasma treatment is used, it is used simultaneously with a thermal treatment at at least 250°C, for instance in the range 250-350°C, and with a UV treatment. Such a combination of indirect plasma, UV and heat are very fast and have a low tendency to damage the 2D material.

[0057] Although a faster treatment is generally a good thing, it is typically more difficult
to control than slower treatments. Slower treatments are therefore also
sometimes advantageously used.

[0058] In embodiments, the UV treatment may comprise exposing the organic sacrificial material to ultraviolet (UV) light having a wavelength between 100 and 300 nm.

[0059] The organic sacrificial material can advantageously be removed in step c, without removing or damaging the 2D material and the metal or ceramic material. In this respect, in embodiments, the metal or ceramic material can advantageously act as a protection or passivation layer for the 2D material.

[0060] In embodiments, the method may further comprise a step a', after step a and before step b, of partially removing the organic sacrificial material. In embodiments, partially removing the organic sacrificial material may comprise leaving a residue of the organic sacrificial material on the 2D material. In embodiments, partially removing the organic sacrificial material may comprise leaving an irreversibly physically adsorbed portion of the organic sacrificial material on the 2D material. In embodiments, step a' may comprise a wet cleaning. In embodiments, the wet cleaning may comprise the use of a solvent suitable for solubilizing the organic sacrificial material. For instance, the solvent may be selected from acetone, acetic acid, toluene, anisole or benzene. These solvents are for instance suitable for solubilizing PMMA. In embodiments, the wet cleaning may comprise dipping the organic sacrificial material in a solvent for at least 1 hour, for instance from 1 to 3 hours. In embodiments, step a' may comprise a plasma treatment. In embodiments, the plasma treatment may comprise an H2 plasma treatment (e.g. H2 remote plasma) or an H2/N2 plasma treatment.

[0061] In embodiments, step c may further comprise removing the metal or ceramic material. In embodiments, removing the metal or ceramic material may comprise a wet etching, e.g. using tetramethylammonium hydroxide (TMAH) or an ammonia-peroxide mixture (APM). TMAH and APM are for instance suitable to remove Al2O3. In preferred embodiments, removing the metal or ceramic material may be performed selectively with respect to the 2D material. The metal or ceramic material can advantageously be removed so as to uncover the 2D material without damaging it or leaving any residue thereon. Indeed, it is easier to remove the metal or ceramic material without damaging the underlying 2D material than removing a sacrificial organic material, in absence of infiltrated metal or ceramic material, without damaging the 2D material.

[0062] In embodiments, step c comprises removing simultaneously both the metal or ceramic material and the organic sacrificial material infiltrated therewith by a wet etching as described supra.

[0063] In embodiments, when the metal or ceramic material is a ceramic material and is not removed in step c, the method may further comprise a step d, after step c, of forming, using the ceramic material as a seed layer, a dielectric layer over the ceramic material. In embodiments, after removing the organic sacrificial material in step c, a layer of the ceramic material over the 2D material may be obtained, said layer being a dielectric layer. In embodiments, the dielectric layer may be a high-k dielectric layer. In embodiments, the dielectric layer may be for use in a semiconductor device (e.g. a transistor). In embodiments, the dielectric layer may be for forming a gate dielectric. In embodiments, the dielectric layer may be conformal with the 2D material thereunder. The ceramic material can advantageously be used, either as such or by using it as a seed layer, to form a (conformal) dielectric layer over the 2D material.

[0064] In a second aspect, the present invention relates to a structure, comprising: (i) a target substrate, (ii) a 2D material on the target substrate, and (iii) a layer over (and typically on) the 2D material, the layer comprising an organic sacrificial material, the organic sacrificial material comprising a metal or ceramic material.

[0065] In embodiments, the layer over the 2D material may comprise an organic sacrificial material infiltrated by a metal or ceramic material. In embodiments, the layer over the 2D material may comprise a metal-infiltrated or a ceramic-material-infiltrated organic sacrificial material.

[0066] In embodiments, any feature of any embodiment of the second aspect may independently be as correspondingly described for any embodiment of the first aspect.

[0067] The invention will now be described by a detailed description of several embodiments of the invention. It is clear that other embodiments of the invention can be configured according to the knowledge of the person skilled in the art without departing from the true technical teaching of the invention, the invention being limited only by the terms of the appended claims.

Example 1: Removing an organic sacrificial material from a 2D material



[0068] We now refer to Fig. 1. A layer of 2D material (200; e.g. an MX2 material such as an MoS2 or a WS2 material) was grown on a host substrate (110).

[0069] We now refer to Fig. 2. A layer of organic sacrificial material (300; e.g. poly(methyl methacrylate), PMMA) was laminated on the 2D material (200). A thermal tape (400) was subsequently bonded to the organic sacrificial material (300).

[0070] We now refer to Fig. 3. The stack of 2D material (200), organic sacrificial material (300) and thermal tape (400) was detached from the host substrate (110).

[0071] We now refer to Fig. 4. The stack of 2D material (200), organic sacrificial material (300) and thermal tape (400) was transferred to the target substrate (120).

[0072] We now refer to Fig. 5. The thermal tape (400) was removed from the organic sacrificial material (300).

[0073] We now refer to Fig. 6. Using a wet treatment (e.g. with acetone) or a plasma treatment (e.g. with H2 (remote) or H2/N2), the organic sacrificial material (300) was partially removed from the 2D material (200). However, some residue (301) of the organic sacrificial material remained on the 2D material (200).

[0074] We now refer to Fig. 7. Using sequential infiltration synthesis (SIS), the residue (301) of the organic sacrificial material is infiltrated with a metal oxide material (311) (e.g. Al2O3). The metal oxide material infiltrates the residue without sticking to the surface of the 2D material. In the case of MX2 being MoS2 or WoS2, without being bound to theory, we believe that this is achieved due to the hydrophobic nature of the S-terminated surface of MoS2 and WoS2.

[0075] We now refer to Fig. 8. The remaining organic sacrificial material residue (310) is removed together with the metal oxide material (311) (in other words, the now metal-oxide material-infiltrated organic sacrificial material residue is removed), e.g. during the wet TMAH treatment. This typically does not require a prior thermal and/or plasma treatment (optionally plus a UV treatment). However, such a prior treatment can be performed.

Example 2: Forming a dielectric layer using the metal or ceramic material as a seed layer



[0076] Example 1 is repeated up to and including Fig. 7.

[0077] We now refer to Fig. 9. The remaining organic sacrificial material residue (310) is removed from the metal oxide material (311), by using a thermal treatment and/or a plasma treatment (optionally in combination with a UV treatment). During these treatments, the metal oxide material (311) may act as a protection/passivation layer for the underlying 2D material (200). Subsequently, using the metal oxide material (311) as a seed layer, a dielectric layer (510; e.g. a high-k material) is deposited over the 2D material (200) using atomic layer deposition (ALD).

Example 3: Forming a dielectric layer from the metal or ceramic material



[0078] Example 1 was repeated up to and including Fig. 5.

[0079] We now refer to Fig. 10. The organic sacrificial material (300) is baked in air for 12-14 hours at a temperature above its glass transition temperature Tg but low enough to avoid calcination. This results in the formation of 1-4 nm thick bottom portion (302) of the organic sacrificial material (300) which is irreversibly adsorbed to the 2D material (200).

[0080] We now refer to Fig. 11. The organic sacrificial material (300) is dipped for 1-3 hours in a solvent (e.g. acetone, acetic acid, toluene, anisole or benzene) to remove the organic sacrificial material which is not irreversibly adsorbed.

[0081] We now refer to Fig. 12. Using SIS, the irreversibly absorbed portion (302) of organic sacrificial material is infiltrated with a metal oxide dielectric material (312; e.g. Al2O3).

[0082] We now refer to Fig. 13. Using a thermal treatment and/or a plasma treatment (e.g. H2/N2) (optionally in combination with a UV treatment), the remaining organic sacrificial material (302) is removed from the metal oxide material (312). In this way, a dielectric layer (520; e.g. a high-k material) comprising the metal oxide material (312) is obtained over the 2D material (200).

Example 4: Forming a dielectric layer from the metal or ceramic material (312) conformally on a structured substrate



[0083] We now refer to Fig. 14. A conformal layer of 2D material (200; e.g. an MX2 material) on a target substrate (130) is provided. The target substrate (130) comprises a 3D structured template layer (132) on a support layer (131).

[0084] We now refer to Fig. 15. A layer of organic sacrificial material (300; e.g. poly(methyl methacrylate, PMMA) is spin-coated over the conformal 2D material (200), thereby forming a planarized layer which overfills the structuring of the template layer.

[0085] We now refer to Fig. 16. The organic sacrificial material (300) is baked in air for 12-14 hours at a temperature above its glass transition temperature Tg but not so high as to trigger calcination. This results in the formation of 1-4 nm thick conformal bottom portion (302) of the organic sacrificial material (300) which is irreversibly adsorbed to the 2D material (200). Subsequently, the organic sacrificial material (300) is dipped for 1-3 hours in a solvent (e.g. acetone, acetic acid, toluene, anisole or benzene) to remove the organic sacrificial material which is not irreversibly adsorbed.

[0086] We now refer to Fig. 17. Using SIS, the portion of organic sacrificial material (302) is infiltrated with a metal oxide dielectric material (312; e.g. Al2O3). Subsequently, using a thermal treatment and/or a plasma treatment (e.g. H2/N2), eventually in combination with a UV treatment, the remaining organic sacrificial material (302) can be removed from the metal oxide material (312). In this way, a conformal dielectric layer (e.g. a high-k material) comprising the metal oxide material (312) is obtained over the 2D material (200).

[0087] It is to be understood that although preferred embodiments, specific constructions, and configurations, as well as materials, have been discussed herein for devices according to the present invention, various changes or modifications in form and detail may be made without departing from the scope and technical teachings of this invention. For example, any formulas given above are merely representative of procedures that may be used. Steps may be added or deleted to methods described within the scope of the present invention.


Claims

1. A method for removing an organic sacrificial material (301) from a 2D material (200), comprising:

a. providing a target substrate (120) having the 2D material (200) thereon and a layer of the organic sacrificial material (301) over the 2D material (200),

b. infiltrating the organic sacrificial material (301) with a metal or ceramic material (311), and

c. removing the organic sacrificial material (301).


 
2. The method according to claim 1, wherein the 2D material (200) is a 2D conductor, a 2D semiconductor or a 2D dielectric.
 
3. The method according to any of the previous claims, wherein the organic sacrificial material (301) is a polymer.
 
4. The method according to any of the previous claims, wherein step b comprises:

b1. exposing the organic sacrificial material (301) to a first precursor, and

b2. exposing the organic sacrificial material (301) to a second precursor.


 
5. The method according to claim 4, wherein the first precursor is a Lewis acidic metal compound and wherein the second precursor is a reductant or an oxidant.
 
6. The method according to any one of the preceding claims, wherein step b comprises a sequential infiltration synthesis.
 
7. The method according to any of the previous claims, wherein step a comprises:

a1. providing a host substrate (110) having thereon the 2D material (200),

a2. covering the 2D material (200) with a layer of organic sacrificial material (300), and

a3. transferring the 2D material (200) and the layer of organic sacrificial material (300) onto the target substrate (120).


 
8. The method according to any of the previous claims, further comprising a step a', after step a and before step b, of:

a'. partially removing the organic sacrificial material (300).


 
9. The method according to any of the previous claims, wherein step c comprises a thermal treatment or a plasma treatment or a UV treatment.
 
10. The method according to any of the previous claims, wherein step c further comprises removing the metal or ceramic material (311).
 
11. The method according to any of claims 1 to 9, further comprising a step d, after step c, of:

d. depositing, using the metal or ceramic material (311) as a seed layer, a dielectric layer (510) over the metal or ceramic material (311).


 
12. The method according to any of claims 1 to 9, wherein, after removing the organic sacrificial material (301) in step c, a layer of the metal or ceramic material (312) over the 2D material (200) results, said layer being a dielectric layer (520).
 
13. The method according to any of the previous claims, wherein the target substrate (120) is a structured substrate (130).
 
14. The method according to any of the previous claims, wherein at least a portion (302) of the organic sacrificial material in step a is irreversibly physically adsorbed to the 2D material (200).
 
15. A structure, comprising:

i. a target substrate (120),

ii. a 2D material (200) on the target substrate (120), and

iii. a layer over the 2D material (200), the layer comprising a metal-infiltrated or ceramic material-infiltrated organic sacrificial material (301).


 




Drawing























REFERENCES CITED IN THE DESCRIPTION



This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

Non-patent literature cited in the description