Self-aligned short-channel electronic devices and fabrication methods of same
11605730 · 2023-03-14
Assignee
Inventors
Cpc classification
H01L29/78681
ELECTRICITY
H01L27/0629
ELECTRICITY
H10K71/16
ELECTRICITY
H10K10/486
ELECTRICITY
H01L29/778
ELECTRICITY
H01L29/24
ELECTRICITY
H01L29/42384
ELECTRICITY
H10K10/466
ELECTRICITY
H01L2029/42388
ELECTRICITY
H01L21/0262
ELECTRICITY
H01L21/02631
ELECTRICITY
H01L27/1288
ELECTRICITY
H01L29/66969
ELECTRICITY
H01L29/41725
ELECTRICITY
H01L29/7606
ELECTRICITY
H01L21/7806
ELECTRICITY
H01L21/02568
ELECTRICITY
H01L29/78696
ELECTRICITY
International classification
H01L21/02
ELECTRICITY
H01L29/24
ELECTRICITY
H01L21/78
ELECTRICITY
Abstract
A self-aligned short-channel SASC electronic device includes a first semiconductor layer formed on a substrate; a first metal layer formed on a first portion of the first semiconductor layer; a first dielectric layer formed on the first metal layer and extended with a dielectric extension on a second portion of the first semiconductor layer that extends from the first portion of the first semiconductor layer, the dielectric extension defining a channel length of a channel in the first semiconductor layer; and a gate electrode formed on the substrate and capacitively coupled with the channel. The dielectric extension is conformally grown on the first semiconductor layer in a self-aligned manner. The channel length is less than about 800 nm, preferably, less than about 200 nm, more preferably, about 135 nm.
Claims
1. A self-aligned short-channel (SASC) electronic device, comprising: a first semiconductor layer formed on a substrate; a first metal layer formed on a first portion of the first semiconductor layer; a first dielectric layer formed on the first metal layer and extended with a dielectric extension on a second portion of the first semiconductor layer that extends from the first portion of the first semiconductor layer, wherein the dielectric extension defines a channel length of a channel in the first semiconductor layer; and a gate electrode formed on the substrate and capacitively coupled with the channel, wherein the substrate comprises a silicon (Si) layer that forms the gate electrode, and an oxidized silicon (SiO.sub.2) layer that forms a gate dielectric layer formed between the first semiconductor layer and the gate electrode.
2. The SASC electronic device of claim 1, wherein the channel length is less than about 800 nm, preferably, less than about 200 nm, more preferably, about 135 nm.
3. The SASC electronic device of claim 1, wherein the gate electrode is formed of highly doped silicon (Si), or a conductive material rather than Si.
4. The SASC electronic device of claim 1, wherein the first semiconductor layer formed of an atomically thin material comprising MoS.sub.2, MoSe.sub.2, WS.sub.2, WSe.sub.2, InSe, GaTe, black phosphorus (BP), or related two-dimensional materials.
5. A circuitry, comprising one or more SASC electronic devices according to claim 1.
6. A self-aligned short-channel (SASC) electronic device, comprising: a first semiconductor layer formed on a substrate; a first metal layer formed on a first portion of the first semiconductor layer; a first dielectric layer formed on the first metal layer and extended with a dielectric extension on a second portion of the first semiconductor layer that extends from the first portion of the first semiconductor layer, wherein the dielectric extension defines a channel length of a channel in the first semiconductor layer; a gate electrode formed on the substrate and capacitively coupled with the channel; and a second metal layer formed on the first dielectric layer and a third portion of the first semiconductor layer that extends from the second portion of the first semiconductor layer.
7. The SASC electronic device of claim 6, further comprising a gate dielectric layer formed between the first semiconductor layer and the gate electrode.
8. The SASC electronic device of claim 7, wherein the gate dielectric layer is formed of oxidized silicon (SiO.sub.2), or a dielectric material rather than SiO.sub.2.
9. The SASC electronic device of claim 6, wherein the substrate comprises a silicon (Si) layer that forms the gate electrode, and an oxidized silicon (SiO.sub.2) layer that forms a gate dielectric layer formed between the first semiconductor layer and the gate electrode.
10. The SASC electronic device of claim 6, wherein the SASC electronic device is a transistor or a contact-doped diode.
11. A self-aligned short-channel (SASC) electronic device, comprising: a first semiconductor layer formed on a substrate; a first metal layer formed on a first portion of the first semiconductor layer; a first dielectric layer formed on the first metal layer and extended with a dielectric extension on a second portion of the first semiconductor layer that extends from the first portion of the first semiconductor layer, wherein the dielectric extension defines a channel length of a channel in the first semiconductor layer; a gate electrode formed on the substrate and capacitively coupled with the channel; a second semiconductor layer formed on the first dielectric layer and a third portion of the first semiconductor layer that extends from the second portion of the first semiconductor layer; a second metal layer formed on a first portion of the second semiconductor layer that is overlapped with the first metal layer; and a second dielectric layer formed on the second metal layer and extended on a second portion of the second semiconductor layer that extends from the first portion of the second semiconductor layer.
12. The SASC electronic device of claim 11, wherein the first and second dielectric layers are formed of a same dielectric material or different dielectric materials.
13. The SASC electronic device of claim 12, wherein the first and second dielectric layers comprise Al.sub.2O.sub.3, HfO.sub.2, ZrO.sub.2, or ZnO.
14. The SASC electronic device of claim 12, wherein each of the first and second dielectric layers is formed by atomic layer deposition (ALD).
15. The SASC electronic device of claim 11, wherein the first and second semiconductor layers are formed of different semiconductors.
16. The SASC electronic device of claim 15, wherein the first semiconductor layer is formed of an atomically thin material comprising one of MoS.sub.2, MoSe.sub.2, WS.sub.2,WSe.sub.2, InSe, GaTe and black phosphorus (BP), and the second semiconductor layer is formed of a second semiconductor comprising BP, WSe.sub.2, or single-walled carbon nanotubes (SWCNTs).
17. The SASC electronic device of claim 11, wherein the SASC electronic device comprises self-aligned van der Waals heterojunctions (vdWHs).
18. The SASC electronic device of claim 11, further comprising a top gate electrode formed on the second dielectric layer.
19. The SASC electronic device of claim 11, wherein the first and second metal layers are formed of a same metallic material or different metallic materials, and serve as a bottom contact (BC) and a top contact (TC) for minimum contact resistance with the first and second semiconductors, respectively.
20. The SASC electronic device of claim 19, wherein each of the first and second metal layers is formed one of gold (Au), titanium (Ti), aluminum (Al), nickel (Ni), chromium (Cr), and other conductive materials.
21. The SASC electronic device of claim 20, wherein the first and second metal layers comprise Au and Ni, respectively.
22. A method for fabricating a self-aligned short-channel (SASC) electronic device, comprising: forming an undercut profile with a bilayer resist on a first semiconductor layer that is formed on a substrate; forming a first metal layer on the undercut profile and the bilayer resist by a directional deposition process; forming a first dielectric layer on the first metal layer by atomic layer deposition (ALD) so that the first dielectric layer on the first metal layer in the undercut profile has a dielectric extension conformally grown on the first semiconductor layer in a self-aligned manner; and forming an encapsulated metal contact in the undercut profile by directional evaporation of metal of the first metal layer on the bilayer resist and lift-off process to remove the bilayer resist, wherein the encapsulated metal contact comprises the first metal covered by the first dielectric layer with the dielectric extension on the first semiconductor, so as to form an SASC electronic device, wherein the dielectric extension defines a channel length of a channel of the SASC electronic device in the first semiconductor layer, wherein the substrate comprises a silicon (Si) layer defining a gate electrode capacitively coupled with the channel.
23. The method of claim 22, wherein the first semiconductor layer is formed of an atomically thin material on an oxidized silicon (SiO.sub.2) layer of the substrate by chemical vapor deposition (CVD).
24. The method of claim 23, wherein the SiO.sub.2 layer is disposed between the gate electrode and the first semiconductor layer.
25. The method of claim 22, wherein the bilayer resist comprises a first resist formed on the first semiconductor layer and a second resist formed on the first resist, wherein the first resist has a molecular weight that is lower than that of the second resist, whereby the first resist has a sensitivity to electron dose being higher than that of the second resist.
26. The method of claim 25, wherein the step of forming the undercut profile with the bilayer resist is formed by electron-beam lithography, such that the undercut profile has a first gap between edges defined by the first resist being wider than a second gap between edges defined by the second resist.
27. The method of claim 22, further comprising forming a second metal layer on the first dielectric layer with the dielectric extension and the first semiconductor layer.
28. The method of claim 27, wherein the step of forming the second metal layer is performed by evaporation of the same metal or a different metal of the first metal layer.
29. The method of claim 27, wherein the SASC electronic device is a transistor or a contact-doped diode.
30. The method of claim 22, further comprising: forming a second semiconductor layer on the first dielectric layer with the dielectric extension and the first semiconductor; forming a second metal layer on a first portion of the second semiconductor layer that is overlapped with the first metal layer; and forming a second dielectric layer on the second metal layer and a second portion of the second semiconductor layer that extends from the first portion of the second semiconductor layer, by the ALD.
31. The method of claim 30, wherein the step of forming the second semiconductor layer on the first dielectric layer with the dielectric extension and the first semiconductor comprises: mechanically exfoliating flakes of a second semiconductor onto a polydimethylsiloxane (PDMS) substrate; and transferring the mechanically exfoliated flakes of the second semiconductor from the PDMS substrate to the first dielectric layer with the dielectric extension and the first semiconductor using a micromanipulator and/or an optical microscope.
32. The method of claim 30, wherein the first and second semiconductor layers are formed of different semiconductors.
33. The method of claim 32, wherein the first semiconductor layer is formed of an atomically thin material comprising one of MoS.sub.2, MoSe.sub.2, WS.sub.2, WSe.sub.2, InSe, GaTe and black phosphorus (BP), and the second semiconductor layer is formed of a second semiconductor comprising BP, WSe.sub.2, or single-walled carbon nanotubes (SWCNTs).
34. The method of claim 30, wherein the first and second dielectric layers are formed of a same dielectric material or different dielectric materials.
35. The method of claim 30, wherein the first and second metal layers are formed of a same metallic material or different metallic materials.
36. The method of claim 30, further comprising forming a top gate electrode on the second dielectric layer.
37. The method of claim 22, wherein the SASC electronic device comprises forming van der Waals heterojunctions (vdWHs).
38. A method for fabricating a self-aligned short-channel (SASC) electronic device, comprising: forming a two dimensional (2D) semiconductor device having a channel length being less than about 200 nm, wherein the 2D semiconductor device comprises: a first semiconductor layer formed of an atomically thin material on a substrate; a first metal layer formed on the first semiconductor layer; and a first dielectric layer formed on the first metal layer and extended with a dielectric extension on the first semiconductor layer, wherein the dielectric extension defines the channel length in the first semiconductor layer, wherein the step of forming the 2D semiconductor device comprises: forming an undercut profile with a bilayer resist on the first semiconductor layer by electron-beam lithography, wherein the bilayer resist comprises a first resist formed on the first semiconductor layer and a second resist formed on the first resist, wherein the first resist has a molecular weight that is lower than that of the second resist, such that the formed undercut profile has a first gap between edges defined by the first resist being wider than a second gap between edges defined by the second resist; directionally depositing a first metal in the undercut profile to form the first metal layer; and ALD growing a first dielectric material on the first metal layer to form the first dielectric layer with the dielectric extension conformally grown on the first semiconductor layer in the undercut profile in a self-aligned manner.
39. The method of claim 38, wherein the step of forming the 2D semiconductor device further comprises: directionally evaporating the first metal on the bilayer resist; and removing the bilayer resist.
40. The method of claim 39, wherein the 2D semiconductor device is a transistor or a contact-doped diode.
41. The method of claim 39, wherein van der Waals heterojunctions (vdWHs) are achieved by transferring another 2D semiconductor device followed by metallization.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) The accompanying drawings illustrate one or more embodiments of the invention and together with the written description, serve to explain the principles of the invention. Wherever possible, the same reference numbers are used throughout the drawings to refer to the same or like elements of an embodiment.
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DETAILED DESCRIPTION OF THE INVENTION
(22) The present invention will now be described more fully hereinafter with reference to the accompanying drawings, in which exemplary embodiments of the present invention are shown. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. Like reference numerals refer to like elements throughout.
(23) The terms used in this specification generally have their ordinary meanings in the art, within the context of the invention, and in the specific context where each term is used. Certain terms that are used to describe the invention are discussed below, or elsewhere in the specification, to provide additional guidance to the practitioner regarding the description of the invention. For convenience, certain terms may be highlighted, for example using italics and/or quotation marks. The use of highlighting and/or capital letters has no influence on the scope and meaning of a term; the scope and meaning of a term are the same, in the same context, whether or not it is highlighted and/or in capital letters. It will be appreciated that the same thing can be said in more than one way. Consequently, alternative language and synonyms may be used for any one or more of the terms discussed herein, nor is any special significance to be placed upon whether or not a term is elaborated or discussed herein. Synonyms for certain terms are provided. A recital of one or more synonyms does not exclude the use of other synonyms. The use of examples anywhere in this specification, including examples of any terms discussed herein, is illustrative only and in no way limits the scope and meaning of the invention or of any exemplified term. Likewise, the invention is not limited to various embodiments given in this specification.
(24) It will be understood that, although the terms first, second, third, etc. may be used herein to describe various elements, components, regions, layers and/or sections, these elements, components, regions, layers and/or sections should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer or section from another element, component, region, layer or section. Thus, a first element, component, region, layer or section discussed below can be termed a second element, component, region, layer or section without departing from the teachings of the present invention.
(25) It will be understood that, as used in the description herein and throughout the claims that follow, the meaning of “a”, “an”, and “the” includes plural reference unless the context clearly dictates otherwise. Also, it will be understood that when an element is referred to as being “on,” “attached” to, “connected” to, “coupled” with, “contacting,” etc., another element, it can be directly on, attached to, connected to, coupled with or contacting the other element or intervening elements may also be present. In contrast, when an element is referred to as being, for example, “directly on,” “directly attached” to, “directly connected” to, “directly coupled” with or “directly contacting” another element, there are no intervening elements present. It will also be appreciated by those of skill in the art that references to a structure or feature that is disposed “adjacent” to another feature may have portions that overlap or underlie the adjacent feature.
(26) It will be further understood that the terms “comprises” and/or “comprising,” or “includes” and/or “including” or “has” and/or “having” when used in this specification specify the presence of stated features, regions, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, regions, integers, steps, operations, elements, components, and/or groups thereof.
(27) Furthermore, relative terms, such as “lower” or “bottom” and “upper” or “top,” may be used herein to describe one element's relationship to another element as illustrated in the figures. It will be understood that relative terms are intended to encompass different orientations of the device in addition to the orientation shown in the figures. For example, if the device in one of the figures is turned over, elements described as being on the “lower” side of other elements would then be oriented on the “upper” sides of the other elements. The exemplary term “lower” can, therefore, encompass both an orientation of lower and upper, depending on the particular orientation of the figure. Similarly, if the device in one of the figures is turned over, elements described as “below” or “beneath” other elements would then be oriented “above” the other elements. The exemplary terms “below” or “beneath” can, therefore, encompass both an orientation of above and below.
(28) Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and the present disclosure, and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
(29) As used in this disclosure, “around”, “about”, “approximately” or “substantially” shall generally mean within 20 percent, preferably within 10 percent, and more preferably within 5 percent of a given value or range. Numerical quantities given herein are approximate, meaning that the term “around”, “about”, “approximately” or “substantially” can be inferred if not expressly stated.
(30) As used in this disclosure, the phrase “at least one of A, B, and C” should be construed to mean a logical (A or B or C), using a non-exclusive logical OR. As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed items.
(31) The description below is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. The broad teachings of the invention can be implemented in a variety of forms. Therefore, while this invention includes particular examples, the true scope of the invention should not be so limited since other modifications will become apparent upon a study of the drawings, the specification, and the following claims. For purposes of clarity, the same reference numbers will be used in the drawings to identify similar elements. It should be understood that one or more steps within a method may be executed in different order (or concurrently) without altering the principles of the invention.
(32) Van der Waals heterojunctions (vdWHs) between two-dimensional (2D) materials such as graphene and MoS.sub.2 have shown promise for low-power tunneling transistors, high-gain photodetectors, and gate-tunable analog applications. However, all methods to date either layer micron-scale flakes in an unscalable manner or use undesired transistors in series with vertical van der Waals heterojuctions that limit their performance.
(33) One of the objectives of this invention is to provide self-aligned short-channel (SASC) electronic devices and generalized self-aligned fabrication methods for a diverse class of electronic devices based on van der Waals layered materials and their heterojunctions.
(34) In one embodiment shown in panel (iv) of
(35) For the first semiconductor layer (semiconductor 1), the second portion extends from the first portion and the third portion extends from the second portion. It should be appreciated that the first, second and third portions are used to differentiate portions on which the first metal layer (metal 1), the dielectric extension and the second metal layer (metal 2) are formed only, and are not structurally different from each other. In one exemplary embodiment, the first semiconductor layer (semiconductor 1) is formed of an atomically thin material, such as MoS.sub.2, MoSe.sub.2, WS.sub.2, WSe.sub.2, InSe, GaTe, black phosphorus (BP), or related two-dimensional materials, on an SiO.sub.2 layer of the substrate by chemical vapor deposition (CVD).
(36) In one embodiment, as shown in
(37) In certain embodiments, the substrate comprises a Si layer or a highly doped Si layer that forms the gate electrode, and an SiO.sub.2 layer that forms the gate dielectric layer formed between the first semiconductor layer and the gate electrode.
(38) As shown in
(39) In another embodiment shown in panel (v) of
(40) Similarly, for the second semiconductor layer (semiconductor 1), the second portion extends from the first portion. It should be appreciated that the first and second portions are used to differentiate portions on which the second metal layer (metal 2) and an dielectric extension of the second dielectric layer are formed only.
(41) In one embodiment, the first and second semiconductor layers are formed of different semiconductors. In one embodiment, the first semiconductor layer is formed of an atomically thin material comprising one of MoS.sub.2, MoSe.sub.2, WS.sub.2 and WSe.sub.2, InSe, GaTe and BP, and the second semiconductor layer is formed of a second semiconductor comprising BP or WSe.sub.2, or single-walled carbon nanotubes (SWCNTs).
(42) In certain embodiments, the first and second metal layers are formed of a same metallic material or different metallic materials, and serve as a bottom contact (BC) and a top contact (TC) for minimum contact resistance with the first and second semiconductors, respectively. In one embodiment, each of the first and second metal layers is formed one of gold (Au), titanium (Ti), aluminum (Al), nickel (Ni), chromium (Cr), and other conductive materials. In one embodiment, the first and second metal layers comprise Au and Ni, respectively.
(43) Accordingly, the SASC electronic device shown in panel (v) of
(44) Another embodiment of the vdWHs is also shown
(45) In one aspect, the invention relates to a circuitry having one or more SASC electronic devices according to the above disclosure.
(46) In another aspect, the invention relates to a method for fabricating an SASC electronic device. Referring to
(47) At first, the first semiconductor layer (semiconductor 1) is formed of an atomically thin material on an SiO.sub.2 layer of the substrate by CVD.
(48) An undercut profile is then formed in a bilayer resist (resist 1 and resist 2) on a first semiconductor layer (semiconductor 1), by electron-beam lithography, as shown in panel (i) of
(49) Further, as shown in panel (ii) of
(50) In addition, as shown in panel (iii) of
(51) Moreover, as shown in panel (iv) of
(52) In certain embodiments, the substrate comprises a silicon layer defining a gate electrode capacitively coupled with the channel, and the SiO.sub.2 layer is disposed between the gate electrode and the first semiconductor layer.
(53) As shown in panel (v) of
(54) In one embodiment as shown in
(55) Furthermore, the method may include forming a top gate (TG) electrode on the second dielectric layer, as shown in
(56) In certain embodiments, the first and second semiconductor layers are formed of different semiconductors. In certain embodiments, the first semiconductor layer is formed of an atomically thin material comprising one of MoS.sub.2, MoSe.sub.2, WS.sub.2 and WSe.sub.2, InSe, GaTe, BP, and the second semiconductor layer is formed of the second semiconductor comprising BP, WSe.sub.2, or SWCNTs.
(57) In certain embodiments, the first and second dielectric layers are formed of a same dielectric material or different dielectric materials.
(58) In certain embodiments, the first and second metal layers are formed of a same metallic material or different metallic materials.
(59) In one embodiment, the SASC electronic device comprises forming van der Waals heterojunctions (vdWHs).
(60) In yet another aspect of the invention, the method for fabricating a SASC electronic device includes forming a 2D semiconductor device having a channel length being less than about 200 nm. The 2D semiconductor device has a first semiconductor layer formed of an atomically thin material on a substrate; a first metal layer formed on the first semiconductor layer; and a first dielectric layer formed on the first metal layer and extended with a dielectric extension on the first semiconductor layer, where the dielectric extension defines the channel length in the first semiconductor layer.
(61) In certain embodiments, the step of forming the 2D semiconductor device includes forming an undercut profile with a bilayer resist on the first semiconductor layer by electron-beam lithography, where the bilayer resist comprises a first resist formed on the first semiconductor layer and a second resist formed on the first resist, where the first resist has a molecular weight that is lower than that of the second resist, such that the formed undercut profile has a first gap between edges defined by the first resist being wider than a second gap between edges defined by the second resist; directionally depositing a first metal in the undercut profile to form the first metal layer; and ALD growing a first dielectric material on the first metal layer to form the first dielectric layer with the dielectric extension conformally grown on the first semiconductor layer in the undercut profile in a self-aligned manner.
(62) In addition, the step of forming the 2D semiconductor device further comprises directionally evaporating the first metal on the bilayer resist, and removing the bilayer resist.
(63) As disclosed above, the self-alignment fabrication method enables the fabrication of source-gated transistors using monolayer MoS.sub.2 with near-ideal current saturation characteristics and channel lengths down to about 135 nm. In addition, self-alignment for van der Waals p-n heterojunction diodes provides complete electrostatic control of both the p-type and n-type constituent semiconductors in a dual-gated geometry, resulting in gate-tunable anti-ambipolar characteristics. The versatility of the fabrication method is further demonstrated via contact-doped MoS.sub.2 homojunction diodes and mixed-dimensional heterojunctions based on organic semiconductors. The fabrication method is scalable to large areas as demonstrated by the fabrication of self-aligned short-channel (SASC) transistors with sub-diffraction channel lengths in the range of about 150 nm to about 800 nm using photolithography on large-area MoS.sub.2 films grown by chemical vapor deposition.
(64) The exemplary implementations of the fabrication methods and SASC devices, and their characterizations are described below in detail.
(65) In certain embodiments of the fabrication method, photolithography and electron beam lithography resists are used to obtain sub-micron undercuts in the resist profiles. Subsequent evaporation of metals and conformal growth of metal oxides by atomic layer deposition results in dielectric extensions as small as about 135 nm. The dielectric extension on the semiconductor defines the channel of a transistor (with the same metal contacts) or homojunction diode (with different metal contacts) as demonstrated with monolayer MoS.sub.2. The fabrication method is modular, which implies that the self-aligned dielectric extension can be applied to other devices such as dual-gated p-n heterojunction diodes as demonstrated with a black phosphorus-MoS.sub.2 heterojunction. Dual gates allow complete electrostatic control of both sides of the heterojunction while minimizing series resistance from the constituent materials. The resulting anti-ambipolar characteristics are highly tunable with potential applications in next-generation integrated circuited technology.
(66) In certain embodiments, the underlying building block of the self-aligned method is a dielectric extension protruding from metal electrodes, which is formed by exploiting resist undercuts that are ubiquitous in lithographic processes. Both electron-beam lithography and photolithography resist undercuts have been optimized to obtain dielectric extensions in the range of about 100 nm to about 800 nm, as shown in
(67) Using this methodology, SASC MoS.sub.2 FETs were fabricated on local gates (Au) 110 on undoped Si wafers with about 300 nm thick thermal oxide 120, as shown in
(68) This behavior is similar to conventional source-gated transistors (SGTs) that evolved from the staggered Schottky Barrier Transistor [12]. SGTs possess increased r.sub.o and intrinsic gain and decreased saturation drain voltage (V.sub.SAT=V.sub.G−V.sub.TH) in comparison to standard FETs [13, 14]. Unlike conventional FETs where the depletion region is formed only near the drain contact [15], the depletion region in SGTs forms first near the source contact at low V.sub.D biases, and another depletion region emerges near the drain contact at higher biases, resulting in nearly ideal current saturation and immunity against short-channel effects such as channel length modulation [13-15]. The device characteristics of conventional SGTs have been explained by three models: gate-induced source barrier lowering [16], series resistance of the depletion region between source and channel [17], and a thermionic emission-diffusion model with current injection concentrated at the edge of the source electrode [14]. However, most conventional SGTs use an amorphous or polycrystalline silicon semiconducting layer with thicknesses (about 100 nm) comparable to the gate dielectric, in contrast to the 0.7 nm thick monolayer MoS.sub.2 used here. Thus, one can expect that the electrostatics and resulting charge transport of the SASC MoS.sub.2 FETs are significantly different from those of previously reported SGTs [14, 16].
(69) To explore the operating principles of the SASC MoS.sub.2 FETs, a device simulator (Sentaurus, Synopsys) was used to model carrier densities, potential distributions, and resulting charge transport for different short-channel device geometries and bias configurations, as shown in
(70) Simulated energy band profiles, as shown in
(71) The self-alignment approach also facilitates the reliable fabrication of p-n vdWHs with small footprints and unique electrostatic gating control. With previously reported fabrication methods, p-n vdWHs, whether lateral or vertical, included a p-n heterojunction connected by two lateral p-type and n-type extensions (acting as FETs in series) or Schottky diodes with graphene, with the overall stack being coupled to one or two gates with alignment errors increasing with each component [3, 4, 8, 9, 20-24]. In the lateral geometry, p-n vdWHs offer electrostatically controlled doping in the constituent semiconductors but suffer from large parasitic resistance from the lateral extensions beyond the junction region [3, 8, 9, 21, 22, 24]. On the other hand, vertical p-n vdWHs that employ a graphene electrode can achieve larger current density at the cost of defect-induced leakage currents, extraneous Schottky barriers, and electrode screening issues [20, 23, 24]. For example, fully vertical BP—MoS.sub.2 and WSe.sub.2—MoS.sub.2 p-n vdWHs using graphene contacts show poor electrostatic control of I.sub.D-V.sub.TG characteristics, as shown in
(72) Given the band alignment between BP and MoS.sub.2, the dual-gated BP—MoS.sub.2 vdWH shows rectifying I-V characteristics with a rectification ratio up to about 50 (limited by the small band gap of BP about 0.4 eV) that can be controlled by both the top and bottom gates, as shown in
(73) Finite-element simulations elucidate how this unique vdWH geometry improves current rectification and enables tunable anti-ambipolar behavior, as shown in
(74) Self-aligned BP—MoS.sub.2 p-n vdWHs readily enable architecture-(iii). In particular, the BP flake is controlled only by the top gate due to screening of the bottom gate by MoS.sub.2. Similarly, the region of the MoS.sub.2 flake directly underneath BP is controlled only by the bottom gate (II), but the rest of the MoS.sub.2 flake (i2) is influenced by both gates, as shown in
(75) According to the invention, a self-aligned approach enables scalable fabrication of short-channel FETs and vdWHs based on 2D semiconductors. The resulting geometry provides a unique electrostatic control over charge transport including exceptional saturation characteristics in short-channel FETs and nearly complete tunability over the anti-ambipolar response in p-n vdWHs with potential implications for signal-processing applications such as frequency-shift keying and phase-shift keying, as shown in
(76) Compared to conventional methods of assembling 2D materials that are not scalable and do not realize ultimate device performance due to suboptimal contact geometries, the invented method integrates standard resist lithography with atomic layer deposition and metal evaporation methods to achieve short-channel devices in a self-aligned manner. The method enables complex device architectures with high conductance and gate-induced electrostatic control, and can be straightforwardly scaled to large areas.
(77) Further, the invention may have the applications in a variety of fields, such as van der Waals heterojunctions, source-gated short-channel transistors with near-ideal current saturation, high bandwidth current amplifiers, high gain photodetectors, and large-area sub-diffraction fabrication of thin-film transistors, and so on.
(78) These and other aspects of the present invention are further described below. Without intent to limit the scope of the invention, exemplary instruments, apparatus, methods and their related results according to the embodiments of the present invention are given below. Note that titles or subtitles may be used in the examples for convenience of a reader, which in no way should limit the scope of the invention. Moreover, certain theories are proposed and disclosed herein; however, in no way they, whether they are right or wrong, should limit the scope of the invention so long as the invention is practiced according to the invention without regard for any particular theory or scheme of action.
Fabrication Method for Self-Aligned Short-Channel Transistor
(79) In this exemplary embodiment, self-aligned device fabrication was realized using both e-beam lithography (EBL) and photolithography. All SASC MoS.sub.2 transistors discussed in
(80) With an EBL-based process, two bilayer resist systems, MMA/PMMA A4 950 (recipe 1) and PMMA A5 495/PMMA A4 950 (recipe 2), were optimized. The magnitude of the resist undercut is better controlled by the reactivity of resist 1 to the development solution than other processing parameters that affect both resist layers. MMA was the most reactive to the development solution and produced an undercut profile that resulted in a dielectric extension on the order of 500 nm as determined by AFM analysis. On the other hand, PMMA A5 495 is only slightly more reactive than PMMA A4 950 because of their different molecular weights, so the undercut profile was reduced, resulting in a dielectric extension of less than about 200 nm, as shown in
(81) In certain embodiments, single-layer MoS.sub.2 crystals were grown on 300 nm SiO.sub.2/Si substrates by chemical vapor deposition (CVD) using a previously described procedure [2]. Specifically, the SASC MoS.sub.2 transistors shown in
(82) Large-area SASC MoS.sub.2 transistors were fabricated using a photolithography-based process exploiting the inherent undercut in single-layer photoresists on a continuous CVD MoS.sub.2 film, as shown in
(83) Using the geometry shown in panel (iv) of
Fabrication Method for Self-Aligned Semi-Vertical Van Der Waals P—N Heterojunction
(84) In this example, for dual-gated vdWHs, the contacts on the second semiconductor are deposited directly on top of the contacts for the first semiconductor, as shown in panel (iv) of
(85) Specifically, self-aligned BP—MoS.sub.2 vdWHs shown in
(86) For dual-gated vdWHs, channel length L for the extension transistor with the first semiconductor is defined by the length of the dielectric extension, whereas L for the transistor with the second semiconductor is defined by the length of the dielectric extension plus the height of the first contact and the height of its encapsulation layer, as shown in
Materials Characterization and Electrical Measurements
(87) Raman and photoluminescence (PL) spectra of the 2D materials, as shown in
Device Simulations
(88) The Sentaurus Technology Computer Aided Design (TCAD) software package (Synopsys, Inc.) [33] was used to model SASC MoS.sub.2 transistors and self-aligned BP—MoS.sub.2 vdWHs by solving the following steady-state coupled differential equations in two dimensions:
(89) TABLE-US-00001 ∇ .Math. (∈∇ϕ) = −q(p − n + N.sub.D − N.sub.A) − ρ.sub.trap Poisson's equation (1) ∇ .Math. {right arrow over (J.sub.n)} qR.sub.net, n Continuity equation (2a) for electrons −∇ .Math. {right arrow over (J.sub.p)} qR.sub.net, p Continuity equation (2b) for holes {right arrow over (J.sub.n)} = −nqμ.sub.n(∇Φ.sub.n) Current equation for (3a) electrons {right arrow over (J.sub.p)} = −pqμ.sub.p(∇Φ.sub.p) Current equation for (3b) holes
where ε is the static permittivity, ϕ is the electrostatic potential, q is the electronic elementary charge, p and n are the hole and electron densities, N.sub.D and N.sub.A are the ionized donor and acceptor concentrations, ρ.sub.trap is the charge density contributed by traps and fixed charges, {right arrow over (J.sub.n)} and {right arrow over (J.sub.p)} are the electron and hole current densities, R.sub.net,n and R.sub.net,p are the net recombination rates for electrons and holes, μ.sub.n and μ.sub.p are the electron and hole mobilities, and Φ.sub.n and Φ.sub.p are the electron and hole quasi-Fermi potentials. The current equations can be simplified to Equations (3a) and (3b) by using the Einstein relation, D.sub.n(p)=kTμ.sub.n(p), that relates the diffusion coefficient D.sub.n(p) to the mobility μ.sub.n(p), which is valid for non-degenerate semiconductors in thermal equilibrium. The model assumes Fermi-Dirac carrier statistics, complete dopant ionization, and a three-dimensional effective density of states (DOS). The finite element simulations incorporating these assumptions have successfully reproduced characteristics of MoS.sub.2 transistors in previous work [3, 34].
Self-Aligned Short-Channel MoS.SUB.2 .Transistors
(90) The simulated device geometry (
(91) The mobility of single-layer MoS.sub.2 is modeled with an empirical expression for monolayer MoS.sub.2,
(92)
relating impurity concentration, N.sub.1, free carrier density, n, and the effective dielectric constant, ε.sub.e, of the dielectric environment whose effect is taken into account with the parameter A(ε.sub.e). In addition, the Caughey-Thomas formula [37] was implemented to account for velocity saturation at high electric fields,
(93)
where μ.sub.MoS2 is the low field mobility determined with the above formula, v.sub.sat is the saturation velocity, F.sub.hfs=|∇Φ.sub.n| is the driving field for electrons within the MoS.sub.2 region, and β is a fitting parameter which defines the transition from low-field to saturation regime. The output characteristics of short-channel nMOSFETs were reproduced with β=1.8 [38], which was also used for SACS MoS.sub.2 FETs.
(94) The transport behavior of the back-gated FET, source-gated SASC FET, and drain-gated SASC FET is compared under the same conditions, as shown in
(95)
Tunneling through the energy barrier was modeled employing the Wentzel-Kramers-Brillouin (WKB) approximation using reported values for degeneracy and carrier effective masses (see Table 1). A positive fixed charge concentration of 2.2×10.sup.12 cm.sup.−2 at the Al.sub.2O.sub.3/MoS.sub.2 interface was found by comparing the experimental V.sub.TH (
(96) TABLE-US-00002 TABLE 1 Material constants for MoS.sub.2 used in the SASC FET. Parameters 1-L MoS.sub.2 Value Reference Film thickness 0.7 nm Bandgap, E.sub.g 2.15 eV [40] Electron affinity, χ 4.2 eV [41] In-plane and out-of-plane dielectric 4.2 [42] constant, ∈.sub.MoS2 K-valley electron effective mass, m*.sub.n 0.51 [43] K-valley hole effective mass, m*.sub.p 0.54 [43] K-valley degeneracies, g.sub.c, v 2 [44] Interface state density, D.sub.it 6.9 × 10.sup.11 cm.sup.−2 this invention Donor concentration, N.sub.D 1.5 × 10.sup.18 cm.sup.−3 fitting parameter Device model parameters Schottky Barrier height at Au/MoS.sub.2 0.33 eV [39] interface, Φ.sub.B Dielectric constant ALD AL.sub.2O.sub.3, ∈.sub.Al2O3 6.5 [45] Mobility model parameters Saturation velocity, v.sub.sat 3 × 10.sup.6 cm s.sup.−1 [46, 47] Parameter β 1.8 [38] Parameter A(∈.sub.e) 0.08 this invention Impurity concentration, N.sub.I 4 × 10.sup.19 cm.sup.−3 this invention
Self-Aligned BP/MoS.SUB.2 .vdWHs
(97) The goal here is to understand the role and interplay of the device geometry, dielectric environment, and bias configuration for electrostatic doping in a vdWH device. The assumption is that electrostatically controlled carrier density governs transport through the vdWH. The experimental I-V curves were qualitatively reproduced using a simplified model (compared to the MoS.sub.2SASC device model). Constant mobilities for BP and MoS.sub.2 are justified with the low intrinsic carrier density of BP and operation in a low-field regime. Band-to-band tunneling at the BP—MoS.sub.2 interface was neglected. Exposure of BP to ambient air was unavoidable during device fabrication and therefore we assume partially oxidized BP with a high impurity concentration. Acceptor and donor type trap states with an exponential distribution were included in the BP (see Table 1). Materials parameters used in the simulations for BP/MoS.sub.2vdWHs are listed in Table 2.
(98) TABLE-US-00003 TABLE 2 Material constants used to simulate BP-MoS.sub.2 vdWHs. Parameters 5 nm BP Value Reference Film thickness 5 nm Bandgap, E.sub.g 0.4 eV [26] Electron affinity, χ 3.6 eV [48] Dielectric constant, ∈.sub.BP 8.3 (out-of-plane) [49] K-valley electron effective mass, m*.sub.n 0.67 [50] K-valley hole effective mass, m*.sub.p 0.52 [50] K-valley degeneracies, g.sub.c, v 2 [51] Interface state density, D.sub.it 6.9 × 10.sup.11 cm.sup.−2 this invention Effective intrinsic density 1.2 × 10.sup.16 cm.sup.−3 Device model parameters Schottky Barrier height at Ni/BP 0.38 eV [52] interface, Φ.sub.B Dielectric constant ALD AL.sub.2O.sub.3, ∈.sub.Al2O3 6.5 [45] Dielectric constant SiO.sub.2, ∈.sub.SiO2 3.9 Interface trap charge density 5.5 × 10.sup.12 cm.sup.−2 Acceptor and Donor type trap state 4 × 10.sup.18 cm.sup.−3 density Mobility model parameters Constant mobility, μ.sub.BP 20 cm.sup.2/Vs [27] Constant mobility, μ.sub.MoS2 5 cm.sup.2/Vs this invention
(99) In sum, a general self-aligned fabrication scheme is reported here for a diverse class of electronic devices based on van der Waals materials and heterojunctions. In particular, self-alignment enables the fabrication of source-gated transistors in monolayer MoS.sub.2 with near-ideal current saturation characteristics and channel lengths down to about 135 nm. Furthermore, self-alignment of van der Waals p-n heterojunction diodes achieves complete electrostatic control of both the p-type and n-type constituent semiconductors in a dual-gated geometry, resulting in gate-tunable mean and variance of anti-ambipolar Gaussian characteristics. Through finite-element device simulations, the operating principles of source-gated transistors and dual-gated anti-ambipolar devices are elucidated, thus providing design rules for additional devices that employ self-aligned geometries. For example, the versatility of this scheme is demonstrated via contact-doped MoS.sub.2 homojunction diodes and mixed-dimensional heterojunctions based on organic semiconductors. The scalability of this approach is also shown by fabricating self-aligned short-channel transistors with sub-diffraction channel lengths in the range of about 150 nm to about 800 nm using photolithography on large-area MoS.sub.2 films grown by chemical vapor deposition. Overall, this self-aligned fabrication method represents an important step towards the scalable integration of van der Waals heterojunction devices into more sophisticated circuits and systems.
(100) The foregoing description of the exemplary embodiments of the invention has been presented only for the purposes of illustration and description and is not intended to be exhaustive or to limit the invention to the precise forms disclosed. Many modifications and variations are possible in light of the above teaching.
(101) The embodiments were chosen and described in order to explain the principles of the invention and their practical application so as to enable others skilled in the art to utilize the invention and various embodiments and with various modifications as are suited to the particular use contemplated. Alternative embodiments will become apparent to those skilled in the art to which the present invention pertains without departing from its spirit and scope. Accordingly, the scope of the present invention is defined by the appended claims rather than the foregoing description and the exemplary embodiments described therein.
LIST OF REFERENCES
(102) [1]. Bower, R. W.; Dill, R. G. IEEE Int. Elect. Dev. Meeting 1966, 12, 102-104. [2]. Bettis Homan, S.; Sangwan, V. K.; Balla, I.; Bergeron, H.; Weiss, E. A.; Hersam, M. C. Nano Lett. 2017, 17, 164-169. [3]. Jariwala, D.; Howell, S. L.; Chen, K.-S.; Kang, J.; Sangwan, V. K.; Filippone, S. A.; Turrisi, R.; Marks, T. J.; Lauhon, L. J.; Hersam, M. C. Nano Lett. 2016, 16, 497-503. [4]. Jariwala, D.; Marks, T. J.; Hersam, M. C. Nat. Mater. 2016, 16, 170-181. [5]. Desai, S. B.; Madhvapathy, S. R.; Sachid, A. B.; Llinas, J. P.; Wang, Q.; Ahn, G. H.; Pitner, G.; Kim, M. J.; Bokor, J.; Hu, C.; Wong, H.-S. P.; Javey, A. Science 2016, 354, 99-102. [6]. Yan, R.; Fathipour, S.; Han, Y.; Song, B.; Xiao, S.; Li, M.; Ma, N.; Protasenko, V.; Muller, D. A.; Jena, D.; Xing, H. G. Nano Lett. 2015, 15, 5791-5798. [7]. Grigorieva, I. V.; Geim, A. K. Nature 2013, 499, 419-425. [8]. Jariwala, D.; Sangwan, V. K.; Seo, J.-W. T.; Xu, W.; Smith, J.; Kim, C. H.; Lauhon, L. J.; Marks, T. J.; Hersam, M. C. Nano Lett. 2015, 15, 416-421. [9]. Jariwala, D.; Sangwan, V. K.; Wu, C.-C.; Prabhumirashi, P. L.; Geier, M. L.; Marks, T. J.; Lauhon, L. J.; Hersam, M. C. Proc. Natl. Acad. Sci. U.S.A. 2013, 110, 18076-18080. [10]. Cheng, R.; Bai, J.; Liao, L.; Zhou, H.; Chen, Y.; Liu, L.; Lin, Y.-C.; Jiang, S.; Huang, Y.; Duan, X. Proc. Natl. Acad. Sci. U.S.A. 2012, 109, 11588-11592. [11]. Liu, H.; Neal, A. T.; Ye, P. D. ACS Nano 2012, 6, 8563-8569. [12]. Hattori, R.; Shirafuji, J. J. J. Appl. Phys. 1994, 33, 612. [13]. Shannon, J. M.; Gerstner, E. G. IEEE Elec. Dev. Lett. 2003, 24, 405-407. [14]. Valletta, A.; Mariucci, L.; Rapisarda, M.; Fortunato, G. JAP 2013, 114, 064501. [15]. Sze, S. M.; Ng, K. K., Physics of Semiconductor Devices. Wiley-Interscience: 2006. [16]. Balon, F.; Shannon, J. M. Sol. Stat. Electron. 2006, 50, 378-383. [17]. Lindner, T.; Paasch, G.; Scheinert, S. IEEE Trans. Electron Dev. 2005, 52, 47-55. [18]. Sporea, R. A.; Trainor, M. J.; Young, N. D.; Guo, X.; Shannon, J. M.; Silva, S. R. P. Sol. Stat. Electron. 2011, 65, 246-249. [19]. Sanne, A.; Ghosh, R.; Rai, A.; Yogeesh, M. N.; Shin, S. H.; Sharma, A.; Jarvis, K.; Mathew, L.; Rao, R.; Akinwande, D.; Banerjee, S. Nano Lett. 2015, 15, 5039-5045. [20]. Lee, C.-H.; Lee, G.-H.; van der Zande, A. M.; Chen, W.; Li, Y.; Han, M.; Cui, X.; Arefe, G.; Nuckolls, C.; Heinz, T. F.; Guo, J.; Hone, J.; Kim, P. Nat. Nanotechnol. 2014, 9, 676-681. [21]. Nourbakhsh, A.; Zubair, A.; Dresselhaus, M. S.; Palacios, T. Nano Lett. 2016, 16, 1359-1366. [22]. Roy, T.; Tosun, M.; Cao, X.; Fang, H.; Lien, D.-H.; Zhao, P.; Chen, Y.-Z.; Chueh, Y.-L.; Guo, J.; Javey, A. ACS Nano 2015, 9, 2071-2079. [23]. Withers, F.; Del Pozo-Zamudio, 0.; Mishchenko, A.; Rooney, A. P.; Gholinia, A.; Watanabe, K.; Taniguchi, T.; Haigh, S. J.; Geim, A. K.; Tartakovskii, A. I.; Novoselov, K. S. Nat Mater 2015, 14, 301-306. [24]. Zhou, R.; Ostwal, V.; Appenzeller, J. Nano Lett. 2017, 17, 4787-4792. [25]. Deng, Y.; Luo, Z.; Conrad, N. J.; Liu, H.; Gong, Y.; Najmaei, S.; Ajayan, P. M.; Lou, J.; Xu, X.; Ye, P. D. ACS Nano 2014, 8, 8292-8299. [26]. Liu, X.; Qu, D.; Li, H.-M.; Moon, I.; Ahmed, F.; Kim, C.; Lee, M.; Choi, Y.; Cho, J. H.; Hone, J. C.; Yoo, W. J. ACS Nano 2017, 11, 9143-9150. [27]. Wood, J. D.; Wells, S. A.; Jariwala, D.; Chen, K.-S.; Cho, E.; Sangwan, V. K.; Liu, X.; Lauhon, L. J.; Marks, T. J.; Hersam, M. C. Nano Lett. 2014, 14, 6964-6970. [28]. Crespo, J. L.; Duro, R. J.; Pena, F. L. IEEE Trans. Instr. & Measure. 2003, 52, 724-732. [29]. Chuang, S.; Battaglia, C.; Azcatl, A.; McDonnell, S.; Kang, J. S.; Yin, X.; Tosun, M.; Kapadia, R.; Fang, H.; Wallace, R. M.; Javey, A. Nano Lett. 2014, 14, 1337-1342. [30]. Jariwala, D.; Sangwan, V. K.; Lauhon, L. J.; Marks, T. J.; Hersam, M. C. ACS Nano 2014, 8, 1102-1120. [31]. Lotsch, B. V. Annu. Rev. Mater. Res. 2015, 45, 85-109. [32]. Zhou, R.; Ostwal, V.; Appenzeller, J. Nano Lett. 2017, 17, 4787-4792. [33]. https://www.synopsys.com [34]. Howell, S. L.; Jariwala, D.; Wu, C.-C.; Chen, K.-S.; Sangwan, V. K.; Kang, J.; Marks, T. J.; Hersam, M. C.; Lauhon, L. J. Nano Lett. 2015, 15, 2278-2284. [35]. Nan, M.; Debdeep, J. 2D Materials 2015, 2, 015003. [36]. Ma, N.; Jena, D. Phys. Rev. X 2014, 4, 011043. [37]. Caughey, D. M.; Thomas, R. E. Proceedings of the IEEE 1967, 55, 2192-2193. [38]. Khakifirooz, A.; Nayfeh, O. M.; Antoniadis, D. IEEE Trans. Electron Dev. 2009, 56, 1674-1680. [39]. Liu, W.; Sarkar, D.; Kang, J.; Cao, W.; Banerjee, K. ACS Nano 2015, 9, 7904-7912. [40]. Zhang, C.; Johnson, A.; Hsu, C.-L.; Li, L.-J.; Shih, C.-K. Nano Lett. 2014, 14, 2443-2447. [41]. Sup Choi, M.; Lee, G.-H.; Yu, Y.-J.; Lee, D.-Y.; Hwan Lee, S.; Kim, P.; Hone, J.; Jong Yoo, W. Nat. Commun. 2013, 4, 1624. [42]. Cheiwchanchamnangij, T.; Lambrecht, W. R. L. Phys. Rev. B 2012, 85, 205302. [43]. Wickramaratne, D.; Zahid, F.; Lake, R. K. J. Chem. Phys. 2014, 140, 124710. [44]. Padilha, J. E.; Peelaers, H.; Janotti, A.; Van de Walle, C. G. Phys. Rev. B 2014, 90, 205420. [45]. Sangwan, V. K.; Jariwala, D.; Filippone, S. A.; Karmel, H. J.; Johns, J. E.; Alaboson, J. M. P.; Marks, T. J.; Lauhon, L. J.; Hersam, M. C. Nano Lett. 2013, 13, 1162-1167. [46]. He, G.; Ghosh, K.; Singisetti, U.; Ramamoorthy, H.; Somphonsane, R.; Bohra, G.; Matsunaga, M.; Higuchi, A.; Aoki, N.; Najmaei, S.; Gong, Y.; Zhang, X.; Vajtai, R.; Ajayan, P. M.; Bird, J. P. Nano Lett. 2015, 15, 5052-5058. [47]. Fiori, G.; Szafranek, B. N.; Iannaccone, G.; Neumaier, D. Appl. Phys. Lett. 2013, 103, 233509. [48]. Edmonds, M. T.; Tadich, A.; Carvalho, A.; Ziletti, A.; O'Donnell, K. M.; Koenig, S. P.; Coker, D. F.; Özyilmaz, B.; Neto, A. H. C.; Fuhrer, M. S. ACS Appl. Mater. & Inter. 2015, 7, 14557-14562. [49]. Nagahama, T.; Kobayashi, M.; Akahama, Y.; Endo, S.; Narita, S.-i. J. Phys. Soc. Japan 1985, 54, 2096-2099. [50]. Qiao, J.; Kong, X.; Hu, Z.-X.; Yang, F.; Ji, W. Nat. Commun. 2014, 5, 4475. [51]. Yuchen, D.; Adam, T. N.; Hong, Z.; Peide, D. Y. 2D Materials 2016, 3, 024003. [52]. Ling, Z.-P.; Sakar, S.; Mathew, S.; Zhu, J.-T.; Gopinadhan, K.; Venkatesan, T.; Ang, K.-W. Scientific Reports 2015, 5, 18000. [53]. Lee, C.; Yan, H.; Brus, L. E.; Heinz, T. F.; Hone, J.; Ryu, S. ACS Nano 2010, 4, 2695-2700.