Patent Application
20180248117
The present application relates to microelectronics. In particular, the present application relates to variable resistance devices and methods of production thereof.
Neuromorphic electronics that mimic the working principles of neuron and synapse behavior may change the computing paradigm, providing cognitive data processing capabilities. Artificial neuromorphic systems are highly productive due to parallel computing and thus tolerant to defects in circuits, consume low energy due to short spike-like electric pulses, and have reduced circuit complexity due to two terminal structures. Analog adaptive electronics may outperform currently used digital computing platforms in tasks such as image recognition, classification, cognitive computation and sensor data processing.
The memristor, a basic component of neuromorphic systems, is an electrical resistance switch with the capability to retain a state of resistance based on the history of applied voltage and flowing current. Memristor devices can store and process information in contrast to conventional integrated circuit technology where switching transistors and memory are separated. There are several classes of memristors, for example two-terminal vertical-stack, two-terminal planar, or three-terminal resistance switches. Based on the switching mechanism the materials can be grouped into two main categories—chemical and physical switches. The first class includes ionic switching materials where anions or cations are considered to be the mobile species utilizing the principles of redox reactions and nanoionics. Anion motion induced by an electric field leads to valence changes of the metal causing the resistance change of the material (such as metal oxides, metal nitrides, metal iodides and metal chalcogenides), while cation-based devices are driven by electrochemically active metals such as copper or silver with the capability of forming an atomic bridge between electrodes. A second category of memristors based only on physical changes include devices relying on magnetic, ferroelectric, electron/hole trapping and phase-change processes. However, both chemical and physical switching mechanisms can also be realized in a single device.
In this section, the main embodiments of the present invention as defined in the claims are described and certain definitions are given.
According to a first aspect of the present invention, a device is disclosed. The device comprises: a first electrode; a second electrode spaced from the first electrode; a switching region positioned between the first electrode and the second electrode, the switching region comprising one or more materials; and an intermediate region positioned between the switching region and the second electrode, wherein the intermediate region is in electrical contact with the switching region and the second electrode.
The device according to the embodiment may be a variable resistance device, for example a memristive device. A memristive device is a device that has a current-voltage (I-V) pinched-hysteresis loop that has a frequency dependent size. The first and second electrodes may comprise any conductive material. The intermediate region is positioned between the switching layer and the second electrode. As it is clear to a skilled person, the electrodes are numbered as “first” and “second” electrodes for clarity purposes only. They may be interchangeable, have similar or different conductive properties and comprise the same or different materials. In the production of this device the electrodes may be deposited in any order.
The device according to the embodiment may be a variable capacitance device.
The intermediate region may be advantageous in providing electrical contact with the switching region and the second electrode, while at the same time preventing unwanted electrical contact between the first and the second electrodes.
According to an embodiment, the device is a memristor.
According to an embodiment, the switching region is in electrical contact with the first electrode via physical contact with the first electrode, and in electrical contact with the second electrode via physical contact with the intermediate region.
The physical contact can also mean a physical proximity sufficient for establishment of an electrical contact.
According to an embodiment, the switching region comprises one or more materials selected from the group of: transition metal dichalcogenides (TMD), partially oxidized TMD, fully oxidized transition metal oxides (TMO) and graphene-like materials.
The TMD materials may be selected from the group of materials with the following chemical formulas: WX2, MoX2, ScX2, TiX2, HfX2, ZrX2, VX2, CrX2, MnX2, FeX2, CoX2, NiX2, NbX2, TcX2, ReX2, PdX2 and PtX2 wherein “X” may be S, Se or Te. The TMO materials may be selected from the group of materials with the following chemical formulas: WOm, MoOn, ScOn, TiOn, HfOn, ZrOn, VOn, CrOn, MnOn, FeOn, CoOn, NiOn, NbOn, wherein “n” has a value of 2 or 3. The graphene-like materials may be selected from the group including graphene oxide and materials with the following chemical formulas: hexagonal BN, AlN, GaN, InP, InAs, BR, BAs, GaP. All of the above materials may be provided into the switching region as combinations of few-layer flakes or other few-layer structures. As a result, the switching region may comprise one or more few-layer materials selected from the groups listed above. For the purposes of this specification, the term “few-layer” refers to a layered structure with 1-10 layers of atoms. The material may be an insulator, a p-type or an n-type semiconductor.
It is clear to a skilled person that the switching region can comprise these materials in any combination, e.g. in homogenous composites' or as separate hybrid layers. In an exemplary embodiment, the switching regions comprise materials in a stack.
According to an embodiment, the switching region has a thickness between 10 and 1000 nanometers.
According to an embodiment, the intermediate region comprises: metal nanowires (NW), polymers or a combination thereof. Metal nanowires may have a solids content in the range of 1-50 weight percent.
The materials according to this embodiment may be used in any combination or individually. For example, the intermediate region may comprise a conducting polymer selected from the group of: polyanilines (PANT), poly(pyrrole)s (PPY), poly(thiophene)s (PT), poly(3,4-ethylenedioxythiophene) (PEDOT), poly(p-phenylene sulfide) (PPS), poly(acetylene)s (PAC), poly(p-phenylene vinylene) (PPV). Alternatively, but not limited to, the intermediate region may comprise metal nanowires embedded in an insulating polymer matrix. The insulating polymer may be acrylic, polyurethane, polysiloxane, epoxy resins, or other suitable organic media.
According to an embodiment, the intermediate region is in electrical contact with the second electrode and with the switching region via one or more electrical contact points.
In an embodiment, these contact points may be sporadic, For example, if metal nanowires are used in the intermediate region, they can provide sporadic contact points throughout interfaces of the intermediate region. Such sporadic electrical contacts can support nanoscale ionic motion channels. The resistance switching may thereby he localized to a small area of the interface.
The intermediate region may serve as a physical barrier providing sporadic contact points or as a barrier for charge carriers tuning the work function of the second electrode and thus changing the Schottky barrier height.
According to an embodiment, the elements of the device are arranged to form a vertical stack. For example, the elements of the device may be arranged to form a vertical stack few-layer based memristor.
In an embodiment, the device may have a first interface between the first electrode and the switching region, and a second interface between the switching region and the intermediate region. One interface of the device may be an ohmic interface with a large density of dopants (e. g. defects or structural imperfections) while the other interface may be electrically resistive with fewer dopants. A large fraction of applied voltage can drop on the resistive interface providing switching, whereas the ohmic interface always remains highly conductive. The functioning of a resistive switch can be based on the Schottky barrier at the interface insulator/metal or semiconductor/metal. The resistance switching mechanism may rely on nano-ionic transport processes associated with redox reactions, or charge trapping/detrapping, or a mixture of these.
According to an embodiment, the switching region comprises one or more detects including structural defects, pores and/or cavities. For example, the defects may be formed during the deposition or at a later stage, e.g. by partial or full oxidation of the materials. Structural defects may affect the switching properties and be advantageous in a menuistive device. Stoichiometry of the materials can be further disturbed by a number of different techniques including thermal annealing, UV treatment, electron beam bombardment, etc. In an embodiment, the structural defects may improve ionic motion involving the oxygen anions.
According to an embodiment, the intermediate region at least partially fills the pores and/or cavities in proximity to the interface between the intermediate region and the switching region. The pores and/or cavities are fabrication defects that occur during deposition or at a later stage and may affect the functioning of the device negatively.
In an exemplary embodiment, the intermediate region can comprise metal nanowires embedded in an insulating polymer matrix and fill the cavities or pores of the switching region near the interface of the two regions. This provides for sporadic contact points by means of the metal nanowires.
According to an embodiment, the switching region comprises a conductive material and an insulating material, and the device is a variable capacitance device. The device according to an embodiment may be a memcapacitor. Memcapacitor means an electrical capacitive switch with a capability to retain a state of capacitance based on the history of applied voltage and passed charge. The variable capacitance device may also have a variable resistance.
In an embodiment, the insulating material is positioned in the switching region so that at least part of the insulating material is in physical contact with the intermediate region. Physical contact can also mean a physical proximity sufficient for establishment of an electrical contact. The insulated material may be positioned on the top of the switching region.
According to an embodiment, the insulating material comprises a material selected from the group of: insulating transition metal dichalcogenides, transition metal oxides and graphene-like materials.
According to an embodiment, the conductive material comprises a material selected from the group of: conductive transition metal dichalcogenides, transition metal oxides and graphene-like materials.
According to an embodiment, the switching region is partially oxidized. In the embodiment the oxidized part of the switching region comprises the insulating material, and the remaining part of the switching region comprises the conductive material.
According to an embodiment, the oxidized part of the switching region is at least partially in physical contact with the intermediate, region.
According to an embodiment, the intermediate region comprises nanowires embedded in an organic material. The nanowires may comprise metal nanowires, metal oxide nanowires or carbonbased nanowires. In an alternative embodiment, other structures such as nanoparticles, nanorods, nanoplates etc. may be used instead of the nanowires. The organic material may comprise, for example, polymer, silicone or resin.
In an embodiment, the intermediate region is in electrical contact with the second electrode and with the insulating material of the switching region via one or more electrical contact points. The contact points may be sporadic.
In an embodiment, elements of the device are arranged to form a vertical stack.
According to a second aspect of the present invention, a method is disclosed. The method comprises: providing a first electrode; depositing on the first electrode a switching region comprising one or more materials; depositing on the switching region an intermediate region comprising metal nanowires and/or polymers; and depositing on the intermediate region a second electrode.
The method according to this embodiment may be, but not limited to, a method for producing or fabricating a variable resistance device, or a method for producing or fabricating a memristor.
As it is clear to a skilled person, the first and second electrodes are numbered only for clarity purposes. According to an alternative embodiment, the method comprises: providing a first electrode; depositing on the first electrode an intermediate region comprising metal nanowires and/or polymers; depositing on the intermediate region a switching region comprising one or more materials; and depositing on the switching region a second electrode.
The one or more materials according to the method may be, but not limited to, few-layer materials.
According to an embodiment, the method further comprises providing a substrate, wherein the first electrode is provided by depositing said first electrode on the substrate. In other words, according to this embodiment a substrate is provided, and the first electrode is deposited on the substrate, followed by depositing a switching region on the first electrode etc. The substrate can be either rigid or flexible including plastic foils.
According to an embodiment, the method further comprises at least partially oxidizing the switching region comprising one or more materials prior to depositing an intermediate region.
Partial or full oxidation may be performed to modify the interface between the one or more materials of the switching region and the intermediate region. A less conductive oxide layer may be formed at the interface of the switching region by oxidation, and thus the electronic switching properties of the resulting device can be improved. Since, for example, transition metal oxides can be difficult to provide as a material to be deposited, the method according to this embodiment may be beneficial for producing such oxides in-situ during deposition.
Partial oxidation may be performed to form an insulating material on top of the switching region.
In an exemplary embodiment, the method comprises at least partially oxidizing the switching region at various temperatures in a range between 100° C. and 500° C.
According to an embodiment, the switching region comprising one or more materials is deposited on the first electrode by at least one of the following deposition techniques: spray-coating, slot-die coating, inkjet printing, thin film transfer, spreading technique, CVD and sputtering.
According to an embodiment, the intermediate region comprising metal nanowires and/or polymers is deposited on the switching region by dispensing, drop-casting, screen printing, offset printing, gravure printing, flexography, inkjet printing, and the similar techniques.
According to an embodiment, the first and second electrodes are deposited by at least one of the following deposition techniques: sputtering, CVD, PVD and printing. In this embodiment, a substrate is provided and the first electrode is deposited on the substrate.
According to an embodiment, at least partially oxidizing the switching region comprises oxidizing the switching region in an environment comprising oxygen by at least one of the following techniques: thermal annealing, laser, plasma, and xenon flash lamp treatment.
In an embodiment, depositing the switching region comprises depositing on the first electrode a conductive material and depositing on the conductive material an insulating material.
As it is clear to a skilled person, the methods according to these embodiments are not limited to the mentioned techniques, and they are indicated for exemplary purposes only.
According to a third aspect of the present invention, an apparatus is disclosed. The apparatus comprises: at least one processor; at least. one memory coupled to the at least one processor, the at least one memory comprising program code instructions which, when executed by the at least one processor, cause the apparatus to perform the methods according to any of the abovementioned embodiments.
For a more complete understanding of example embodiments of the present invention, reference is now made to the following descriptions taken in connection with the accompanying drawings in which:
Exemplary embodiments of the present invention and its potential advantages are understood by referring to
The device further comprises an intermediate region 103 and a second electrode 104. The intermediate region 103 is in electrical contact with the second electrode 104 and the switching region 102. The intermediate region 103 can comprise, for example, metal nanowires, or a variety of conducting polymers (described above), composite polymers with different conductive fillers such as Carbon Nanotubes, graphene, graphite, metal particles etc. In an exemplary implementation of the device shown in
Typically, a variable resistance device (such as a memristor) is built from a metal/insulator/metal or metal/semiconductor/metal thin-film stack. Due to the nature of some insulators that exhibit memristive properties, the bottom and top electrodes might he shorted in conventional devices, which can potentially render the device unusable. This risk is even more significant when few-layer materials are used in the switching region 102. The intermediate region 103 can prevent this unwanted electrical contact between the electrodes 101 and 104. For example, metal nanowires embedded in polymer matrix can act as a separator that partially fills the pores and cavities in proximity of the interface between the intermediate and the switching regions with insulating polymer, and provides sporadic electrical contacts by nanowires which support ionic motion channels at nanoscale. Therefore, with the intermediate region 103 (for example, comprising metal nanowires 105) unwanted connection between the electrodes of the device is unlikely, and the performance of the device is improved at the same time. According to an embodiment, the intermediate region may be used for tuning of the Schottky barrier properties at the interface between semiconductor and metal.
The conductive material 106 may comprise conductive transition metal dichalcogenides (TMD), transition metal oxides (TMO) and graphene-like materials. The insulating material may comprise insulating TMD, TIVIO and graphene-like materials. The TMD may be any of WX2, MoX2, ScX2, TiX2, ZrX2, VX2, CrX2, MnX2, FeX2, CoX2, NiX2, NbX2, TcX2, ReX2, PdX2, PtX2 wherein X is S, Se or Te. The TMO may be any of WOn, MoOn, ScOn, TiOn, HfOn, ZrOn, VOn, CrOn, MnOn, FeOn, CoOn, NiOn, NbOn, wherein n is 2 or 3. Graphene-like materials may be any of: graphene oxide, h-BN, AlN, GaN, InN, InP, InAs, BP, BAs, and GaP.
The thickness of the conductive material may vary from 1 nm to 1000 nm.
The thickness of the insulating material may vary from 1 nm to 20 am.
The switching region 102 can be partially oxidized, and the oxidized part of the switching region can comprise the insulating material 107, while the remaining part of the switching region can comprise the conducting material 106. In an embodiment, material in the top part of the switching region 102 which is physical contact or proximity to the intermediate region can be oxidized and form the insulating part 107, while the non-oxidized material below can form the conductive part 106.
The intermediate region of the device shown on
Capacitive property of the device is supported by the insulating material stacked between conducting electrodes. The device has a non-linear capacitance with respect to the voltage applied across the electrodes 104, 101. A memory effect originates from changes in permittivity under the external electric field. Electrically-induced ion motion can cause a change of the dielectric constant of the insulating material and thus supports multistate capacitive switching. Nanoionic transport can be fueled by the nature of the materials with intrinsic anion vacancies. When a voltage is applied to the electrodes 101, 104 the electric field can cause the ion motion which changes the permittivity of the insulating material 107 leading to virtual propagation of e.g. the first, electrode 101 towards the second 104. Other switching mechanisms based on physical processes such as carrier charge trapping/detrapping can also be achieved. Memcapacitive and memristive effects may appear simultaneously, for example at nanoscale. In this case capacitive switching and resistive switching may be associated with the same state variables.
A classical approach to memristor fabrication usually requires a high-precision mask alignment and an involvement of high temperatures and low vacuum processes. With the growth of printed electronics industry aligned with the advantages of reducing manufacturing costs, there is a need for solution-processable materials and low-cost technologies that can be applied to manufacturing of memristor arrays.
The method according to the present invention may include an additional step of partial or full oxidation of the materials of the switching region. After the oxidation is performed, the intermediate region 213 is deposited onto a partially or fully oxidized switching region 215 of the structure 205 and the method continues similarly to the embodiment described above. A variety of oxidation techniques can be used including, but not limited to, thermal annealing, laser, plasma, and xenon flash lamp treatment. The gaseous atmosphere of the oxidation can be, for example air, oxygen, ozone or a mixture of an inert gas with oxygen. Ozone atmosphere may enhance the rate and the degree of oxidation during the treatment. Masking may also be used during oxidation in any of the above gaseous atmospheres.
A less conductive oxide layer may be formed at the interface of the switching region 212 by oxidation, which allows improving the electronic switching properties of the resulting device. The partial or full oxidation of materials may also significantly increase the number of defects in the material, which can be beneficial for producing enhanced ionic motion involving the oxygen anions. This allows using, for example, few-layer materials as anion-driven memristors wherein the resistance switching is governed by a variety of defects in the materials that alter electronic transport. While bulk material memristors often require forcible disturbance of stoichiometry in order to achieve sufficient ionic motion, few-layer materials may have natural defects due to their unique structure.
An insulating oxide layer may be formed at the interface of the switching region 212 by oxidation, which allows using the method in production of memcapacitors. Alternatively, deposition of the switching region may comprise depositing on a conductive material first and then depositing an insulating material on top of the conductive material e.g. by vacuum techniques or printing methods. This also allows production of variable capacitance devices by the method.
“Memristance”, or memristive property, can be expressed as a charge-dependent rate of magnetic flux φ with charge q by the following formula M(q)=dφ/dq. Due to the fact that voltage V is a time function of magnetic flux and current I is a time function of charge, the following expression can be obtained: M(q(t))=V(t)/I(t). This shows that memristance is essentially a charge-dependent resistance. With little changes in M(q(t)) under pulsating current conditions the memristor may behave as a resistor. Usually, three main properties of a memristor are considered: 1 pinched 1-V (current-voltage) hysteresis loop; 2—hysteresis lobe area decrease with increase in frequency; and 3—hysteresis loop shrinks to a single-valued function at infinite frequency. The devices described in the following examples are memristors based on few-layer WS2 and MoS2 with a metal nanowire interlayer, deposited by different methods and at different conditions. According to a first exemplary implementation of the method, the first electrodes used in these examples were planar gold electrodes. WS2 and MoS2 flakes dispersed in ethanol solution were spray-coated over the electrode at different temperatures (150° C., 250° C. and 400° C.), and then dried in vacuum. The lateral size of WS2 flakes was 50-150 nm, the thickness was 1-4 monolayers. The lateral size of MoS2 flakes was 100-400 nm, the thickness was 1-8 monolayers. The overall thickness of the switching region was in the range of 50-300 nm. Then, an intermediate region of silver nanowires (NW) dispersed in an organic media was drop-casted. The top electrode was printed using a silver paste. According to the second exemplary implementation of the method, the first electrode was fabricated by screen printing or inkjet printing of silver ink on a polyethylene naphthalate (PEN) substrate. The WS2 and MoS2 thin films were deposited over the electrode by a spreading technique, in particular a modified Langmuir-Blodgett method, where the inorganic film is collected at a polar-nonpolar liquid interface by mixing and then, utilizing a tendency of the interface film to spread or cover any available area, it was transferred to the plastic foil with the printed electrode. The film transfer procedure can be repeated 2-10 times depending on the required film thickness. The overall thickness of the switching region was in the range of 30-300 nm. Then the films were dried in vacuum and annealed at 180-200° C. for 3 hours in air. This led to the formation of an ultrathin oxide layer (˜2-10 nm) at the top surface of the film, resulting in WS2/WOx (x<3) and MoS2/MoOx (x<3) films, respectively. Then, an intermediate region of silver nanowires (NW) dispersed in an organic media was drop-casted. The top electrode was screen printed using a silver paste.
One application of memristors is their function as an analogue of a biological synapse where the strength of the synaptic connection can he precisely changed to perform information processing, learning and memorization in accordance with pre-synaptic and post-synaptic neuron actions. Similarly to synapse terminology, two types of memristor plasticity can be identified: short-term plasticity (STP), in which the changes in resistance last for only seconds and then the memristor returns to the original state, and long-term plasticity (LTP), in which the resistance change can last from hours to years. Memristance is managed by the pulse amplitude, the number of pulses, and input frequency, which all cumulatively change the “synaptic weight” of memristor.
An apparatus in accordance with the invention may include at least one processor in communication with a memory or memories. The processor may store, control, add and/or read information from the memory. The memory may comprise one or more computer programs which can be executed by the processor. The processor may also control the functioning of the apparatus. The processor may control other elements of the apparatus by effecting control signaling. The processor may, for example, be embodied as various means including circuitry, at least one processing core, one or more microprocessors with accompanying digital signal processor(s), one or more processor(s) without an accompanying digital signal processor, one or more coprocessors, one or more multi-core processors, one or more controllers, processing circuitry, one or more computers, various other processing elements including integrated circuits such as, for example, an application specific integrated circuit (ASIC), or field programmable gate array (FPGA), or some combination thereof. Signals sent and received by the processor may include any number of different wireline or wireless networking techniques.
The memory can include, for example, volatile memory, non-volatile memory, and/or the like. For example, volatile memory may include Random Access Memory (RAM), including dynamic and/or static RAM, on-chip or off-chip cache memory, and/or the like. Non-volatile memory, which may be embedded and/or removable, may include, for example, read-only memory, flash memory, magnetic storage devices, for example, hard disks, floppy disk drives, magnetic tape, etc., optical disc drives and/or media, non-volatile random access memory (NVRAM), and/or the like. If desired, the different functions discussed herein may be performed in a different order and/or concurrently with each other. Furthermore, if desired, one or more of the above-described functions may be optional or may be combined.
Although various aspects of the invention are set out in the independent claims, other aspects of the invention comprise other combinations of features from the described embodiments and/or the dependent claims with the features of the independent claims, and not solely the combinations explicitly set out in the claims.
It is also noted herein that while the above describes example embodiments of the invention, these descriptions should not be viewed in a limiting sense. Rather, there are several variations and modifications which may be made without departing from the scope of the present invention as defined in the appended claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| PCT/RU2014/000316 | Apr 2014 | RU | national |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 15305205 | Oct 2016 | US |
| Child | 15962546 | US |
