Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
  • H01L29/40—Electrodes ; Multistep manufacturing processes therefor
  • H01L29/41—Electrodes ; Multistep manufacturing processes therefor characterised by their shape, relative sizes or dispositions
  • H01L29/423—Electrodes ; Multistep manufacturing processes therefor characterised by their shape, relative sizes or dispositions not carrying the current to be rectified, amplified or switched
  • H01L29/42312—Gate electrodes for field effect devices
  • H01L29/42316—Gate electrodes for field effect devices for field-effect transistors
  • H01L29/4232—Gate electrodes for field effect devices for field-effect transistors with insulated gate
  • H01L29/42324—Gate electrodes for transistors with a floating gate
  • H01L29/42332—Gate electrodes for transistors with a floating gate with the floating gate formed by two or more non connected parts, e.g. multi-particles flating gate
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
  • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
  • H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
  • H01L29/76—Unipolar devices, e.g. field effect transistors
  • H01L29/772—Field effect transistors
  • H01L29/78—Field effect transistors with field effect produced by an insulated gate
  • H01L29/788—Field effect transistors with field effect produced by an insulated gate with floating gate
  • H01L29/7881—Programmable transistors with only two possible levels of programmation
  • H01L29/7883—Programmable transistors with only two possible levels of programmation charging by tunnelling of carriers, e.g. Fowler-Nordheim tunnelling
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
  • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
  • H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
  • H01L29/76—Unipolar devices, e.g. field effect transistors
  • H01L29/772—Field effect transistors
  • H01L29/78—Field effect transistors with field effect produced by an insulated gate
  • H01L29/788—Field effect transistors with field effect produced by an insulated gate with floating gate
  • H01L29/7888—Transistors programmable by two single electrons

Definitions

• the present invention concerns transistors. More particularly, the invention concerns single electron technology transistors, being transistors in which one-by-one transport of electrons controls device operation.
• Transistors are the basic building block of electronic devices. The power of a transistor depends, in large part, on its switching speed and its power requirements. Faster switching transistors offer improved performance. Transistors having lower power requirements offer energy conservation and reduced heating. The latter effects are especially important in devices which rely upon self contained power sources.
• the power required to switch a transistor is a function of the amount of current necessary to cause device operation.
• Much research has been conducted in an effort to reduce the amount of current.
• the end goal is a device in which operation is caused by a single electron.
• single electronics single electron technology
• device operation is based on the concept of one carrier for one bit of information. That is, it is based on one-by-one manipulation of electrons through a small sub-structure, and specifically a transistor.
• American researchers first made a transistor that relies on a single electron about fifteen years ago, employing techniques used to make advanced semiconductor chips. They also built a single electron device in which a semiconductor substrate is coated with a thin layer of an insulating material and sprayed minute blobs of indium onto it.
• the present invention concerns a transistor including silicon nanoparticles (diameter ⁇ lnm) .
• the silicon nanoparticles occupy a gate region of the transistor.
• the resulting transistor is a transistor in which single electron flow controls operation of the transistor. Room temperature operation is possible with the novel transistor structure by radiation assistance, with radiation being directed toward the silicon nanoparticles to create necessary holes in the quantum structure for the flow of an electron.
• the transistor of the invention also forms the basis for a memory device.
• the device is a flash memory device which will store electrical charge instead of magnetic effects.
• FIG. 1 depicts an experimental configuration where the tip of a scanning tunneling microscope is placed over a film material at a constant height to simulate a two terminal device;
• FIG. 2 is the I-V response where the tunneling current was recorded while the voltage of the tip was varied with respect to the (grounded) substrate in the range -6 to +3 eV;
• FIG. 3 gives the derivative of the I-V curve, shown in FIG. 2;
• FIG. 4 is the I-V response of the experimental set up of FIG. 1, taken with the radiation from a mercury lamp;
• FIG. 5 is the derivative of the I-V curve of FIG. 4;
• FIG. 6 is an exemplary single electron silicon nanoparticle transistor of the invention;
• FIG. 7 is an exemplary flash memory device of the invention, depicted in cross-section;
• FIG. 8 illustrates a silicon nanoparticle gun
• FIGS. 9a-9c depict operations of the FIG. 7 memory device
• FIG. 10 illustrates a method for forming silicon nanoparticles.
• DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention concerns single electron transistor devices which rely upon elemental silicon nanoparticles.
• the silicon nanoparticles provide a set of discrete levels for electron capture with energy spacing much larger than the thermal fluctuation energy.
• Silicon nanoparticles of diameter ⁇ 1 nm have a discrete set of states resulting from the quantum mechanical wave-like nature of electrons, capable of capturing/emitting single charge carriers, with an energy spacing on the order of 1 electron volt, and a discrete set of electric charging potential energy of 0.24 eV spacing.
• the I-V spectra taken using a scanning tunneling microscope, show single electron charging effects at a spacing of ⁇ 0.26 eV.
• near one hundred percent resolved single electron conductance resonance are observed with a spacing consistent with the spacing of the energy levels of the quantum dots (the nanoparticles). This development permits single electron transistors that operate at room temperatures with radiation-assistance.
• the discrete set of states resulting from the quantum mechanical wavelike nature of electrons in the silicon nanoparticles is capable of capturing/ emitting single charge carriers.
• d ⁇ 1 nm, providing an energy spacing of 1 electron volt, five decades greater than room temperature thermal energy fluctuations (0.025 electron Volt). Only thermal fluctuations at temperatures approaching 12,000 C, more than twice the temperature on the surface of the sun, may interfere with the single electron processes in the particles.
• transistor devices utilizing the particles of the invention will maintain single electron processes comfortably at room temperature or any other temperature encountered under laboratory or real field conditions. Such transistor devices are truly high temperature single electronics devices.
• the spacing of the energy states is a sensitive function of the diameter of the particle (quadratic dependence). For a particle of 6 nm diameter, the spacing drops to 0.027 of an electron volt. For this size, fluctuations at room temperature are equal to the energy of single electron processes. Thus, to ensure high quality operation at room temperature, sizes reasonably below 6 nm must be used. Even for 6 nm, the device must be cooled to liquid nitrogen temperature to exhibit reasonably resolved single electron processes. Thus, it is preferred that transistor devices of the invention use silicon nanoparticles having approximately 1 nm diameters.
• the potential energy due to the discreteness of the charge is therefore more important for larger sizes. At intermediate sizes, the two become comparable.
• the quantum energy dominates, however, for the silicon nanoparticles used in the present transistor.
• the single electron devices become operational at a given temperature if at least one of the two of these discrete systems dominate the energy of thermal fluctuation.
• the characteristic charging unit is 0.24 eV, smaller than the quantum energy ( 1 e V) . But both are much larger than thermal fluctuation energy for room temperature (0.025 eV).
• the discreetness, hence the single electron processes, are also maintained at elevated temperatures as high as 12,000C.
• the silicon nanoparticle of ⁇ lnm diameter is essentially non conducting because all of the electronic energy levels are filled with stationary electrons. Standard doping levels of 10 15 / cm 3 boron atoms allocates only 10 "6 electron vacancies per particle (essentially none). Even strong doping at a level of 10 17 /cm 3 would be insufficient. The lack of non conductivity, however, will not hamper the operation of the high temperature device based on the single electron charging effects.
• the present invention provides means to create vacancies for electrons to be captured by the quantum energy levels, rendering single electronics operational at high temperatures via both the discreteness of energy and the single electron charging. Irradiation of the silicon nanoparticles creates the necessary vacancies for single electron operation.
• FIG. 1 depicts the experimental configuration where a tip 12 of the scanning tunneling microscope 10 is placed over a silicon nanoparticle film material 14 on a substrate 16 at a constant height. Silicon nanoparticles 18 contained in the film 14 are represented with an exaggerated dimension by the particle 18 in FIG. 1. In this two-terminal arrangement, the tip 12 acts as the source, while the substrate 16 acts as the drain. We probed the conductance of the particles by recording the I-V spectra of the film 14.
• the FIG. 1 configuration may be represented by a double barrier model.
• the particles 18 represent the quantum well, with a vacuum barrier due to a gap between the particle and the tip 12, and a barrier due to a gap between the particles 18 and the substrate 16.
• the tunneling current was set at 1 nA and the biasing voltage at 3 V in a constant current mode, giving a tip height of several angstroms.
• the feedback loop was then disengaged allowing the tip 12 to be held in a constant height mode while taking the I-V spectra. While the voltage of the tip was varied with respect to the (grounded) substrate 16 from -6 to + 3 volts, the tunneling current was recorded.
• FIGS. 2-5 The measurement results are given in FIGS. 2-5.
• FIG 2 is the I-V response where the tunneling current was recorded while the voltage of the tip was varied with respect to the (grounded) substrate in the range -6 to +3 eV with no light stimulus.
• the staircase due to charging is discemable, but not easily resolved.
• FIG.2 gives an average of sixteen individual spectra. Averages over a larger number tend to exhibit drifts due to difficulty in maintaining a constant tip height, which may wash out the structure.
• FIG. 3 the derivative of the FIG. 2 I-V curve, clearly shows a progression of resonances at a spacing of 0.26 eV for both positive and negative tip biasing with respect to the substrate.
• FIG. 1 To investigate the effect of light stimulation, data was also taken with the FIG. 1 experimental set-up, with the film 14 containing nanoparticles 18 being stimulated by the light from a mercury lamp.
• the radiation spectral width spans the range 300 nm to 600 nm with a maximum at 350.
• a Pyrex glass port through which the mercury stimulation light is coupled to the vacuum system has a transmittance cutoff at 270 nm.
• the I-V response shown in FIG. 4, now shows quite visibly a second regular step structure superimposed on the spectrum taken under darkness conditions with no light stimulus as in FIGS. 2 and 3.
• T e « r c the charge is not accumulated in the particles and the only visible structure is the one related to energy quantization.
• the energy quantization structure with larger period modulates the charging related superfine structure with smaller period.
• the modulation period is increased due to charge accumulation, and equals ⁇ + 2 ⁇ . Since the period measured for the discreteness of energy is equal to the atomic transitions, then it is concluded that T e and T c are comparable.
• FIG. 6 gives a schematic of the field effect transistor with the nanoparticles implanted in the gate oxide as a buried gate. It shows the source, drain, and gate electrodes 17a, 17b and 17c, with electric leads for voltage biasing, and it shows the nanoparticle floating buried gate (shown outside the gate area for purposes of illustration).
• the buried nanoparticle gate 18a is connected to a voltage source, thus it can be biased independent from the source-drain-external gate, or it can be used as floating gate with no biasing.
• the source-drain conductance may be directly derived from the I-V characteristic measured using a precision semiconductor parameter analyzer. The characteristic are measured while the source is grounded and the drain voltage fixed at 1 mV.
• the source-drain conductance oscillates when the gate voltage is varied if the particle size is such that single electron charging or the quantum energy spacing dominates thermal energies. The oscillation period is the single electron charging or quantum energy spacing.
• silicon nanoparticles 18 are implanted in the gate area 20 of a Si MOSFET as a buried gate layer. Lateral transport across the source-drain channel of the transistor, through the particles, would exhibit single electron effects as a function of the gate biasing. UV irradiation can be used to switch the single electron operation.
• This device may act as a dual electrical and optical device.
• the nanoparticles may be photo or electro stimulated to produce blue laser beams within the body of the transistor. At the same time, it will operate as a single electronics device.
• tunneling from the particle gate to the substrate or drain is slowed down by providing sufficient insulators such that r c « T e , then the transistor will act as a memory device.
• Silicon particle floating flash memory devices operate on the use of media that store electric charge instead of using media that store magnetic effects. This requires electrical isolation of the sub elements of the media from each other and from the connection to the powering elements (source-drain). Silicon islands (particles or so called quantum dots) which are electrically floating (electrically insulated from every other element) within the volume of the insulating oxide of the gate of a field effect transistor are the backbone of this device, shown in FIG. 7.
• FIG. 7 is a schematic cross section of a nanoparticle memory device, showing the source 30, drain 32, and the gate 34 of the device.
• the silicon nanoparticles 18 are sandwiched between a thin oxide 36 of 1-2 nm thickness (tunneling oxide) that has been grown on the channel face, and a somewhat thicker control oxide ( ⁇ 5 to 10 nm) grown over the particles.
• the device of FIG. 7 offers fast-access, low-power dissipation, and possible extreme down-scaling. As the race to extreme down-scaling of device size continues to achieve faster and more efficient devices, and dense packing, it is important to develop methods for synthesis of small enough silicon floating gates (particles) to be accommodated within the gate oxide.
• the fabrication technology must keep up with the down-scaling, such that it will become possible for the floating gates in flash memory to be reduced to the nanometer scale, effectively behaving like quantum dots. If so, then it will be fabricated with a minimum perturbation of conventional silicon technology, and operate at room or higher temperature.
• the ultra-small size of the nanoparticles of the invention allows the realization of such technology.
• the deposition (sandwiching) the particles in the gate oxide may be accomplished using a Si nanoparticle gun.
• the gun delivers the particle's onto the gate area simultaneously with the deposited control oxide.
• the concept of the particle gun is similar to an ion beam gun used for ion implantation.
• the particles energy need not be as high since they are to be deposited and not implanted.
• a colloid of the particles in a volatile liquid such as acetone, or alcohol
• a jet or stream of the colloid is leaked into the system.
• Amechanism such as a plasma, or a radiation source is used to electrically charge the particles. The particles will then be accelerated to the required energy.
• a Mass filter is used for size selectivity and to reject any residual material from the solvent.
• a particle gun may be constructed as shown in FIG. 8.
• the gun includes a Si nanoparticle inlet 38 to deliver the particles.
• the inlet 38 which may be an atomizer, utilizes a colloid of the Si nanoparticles in a volatile liquid (such as acetone, water, or alcohol).
• a jet or stream of the colloid is shot or leaked into the Si particle ion source 40 of the gun. Most of the volatile solvent droplets will evaporate leaving the Si particles in flight. In the ion source 40, the particles get charged in their flight.
• the produced particle ions are accelerated (propelled) into a focusing lens 42, powered by a feedthrough electrical connection 44, where they get focused, collimated and accelerated.
• the accelerated particles enter into a velocity filter 46 for mass (size) selection and rejection of nonsilicon species such as residual solvent material.
• the velocity filter 46 is powered through a feedthrough 47 (some feedthroughs, e.g., a feedthrough for the inlet 38 are not pictured in FIG. 8 for simplicity of illustration).
• Mass selection is important to ensure that there is no material from the solvent in the Si nanoparticle beam. A mass selectivity of ⁇ 2/1000 can be achieved.
• the particle energy at the exit of the velocity filter 46 is in the range 500 to 10 keV.
• the particle beam enters a decelerator 48 which is capable of lowering the energy of the particles, delivering mass (size) selected particles with energies less than 500 eV (as low as 1 eV), though the deceleration 48 may be omitted if exit velocity is not a concern.
• Vacuum in the gun of FIG. 8 is monitored and controlled through vacuum port 50.
• the memory device of FIG. 7 may be built by such techniques using a N-channel or a p-channel Si material.
• N-channel memory where the channel is rich in excess electrons, biasing the gate positive relative to the source (grounded), and to the drain (biased at ⁇ 0.1 Volt) attracts electrons from the channel to tunnel through the thin oxide and charge the silicon nanoparticles (write step), as shown in FIGS. 9a-9b.
• Reversal of the charge from the silicon nanoparticles back to the channel may be achieved by reversing the polarity of the gate bias (erase step), as shown in FIG 9c.
• the number of charges that may be accommodated on each silicon nanoparticle depends on the size of the silicon nanoparticle and on the biasing of the gate relative to the source-drain. Large gate voltages lead to an increase in the number of stored electrons. Smaller silicon nanoparticle sizes lead to a large single electron charging, thus limiting the number of electrons.
• biasing the gate negative relative to the source and to the drain attracts holes from the channel to tunnel through the thin oxide and charges the particles in the writing step. Erasure is achieved by reversing polarity of the gate voltage.
• the effective memory threshold voltage shift that retains the charge on r, _ ⁇ l nt o , 1 1 nd the particles is given by the simple expression: ⁇ ° £p , where n is the surface density of the nanoparticles, q is the electronic charge, tO is the thickness of the control oxide, d is the diameter of the nanoparticle, and ⁇ 0 and ⁇ -, are the permittivities of the oxide and the particle respectively.
• n the surface density of the nanoparticles
• q the electronic charge
• tO the thickness of the control oxide
• d the diameter of the nanoparticle
• ⁇ 0 and ⁇ - are the permittivities of the oxide and the particle respectively.
• the ultra-small particles of the invention provide several advantages to transistor technology. First, they can be accommodated in extremely down-scaled transistors. Second, our preparation and colloid filtering, along with the mass analysis provided by the particle gun delivery system provide a high quality control on the definition and selection of the size. A narrow mass distribution ( ⁇ 0.25%) ensures that the discrete energy system is well defined and that the device threshold is sharp. Large variations in the size of an ensemble of particles turns the discrete spectrum into a quasi continuum and washes the device threshold. Previously, sizes smaller than 5 nm have not been achieved, and the size fluctuation exceeds 5 to 10 percent. Third, the particles are very small such that the single electron charging and the quantum energy spacing is larger than the thermal energy, thus single electron processes are in operation at room or higher temperature.
• the particles may be operated as a multi-level memory system.
• the single electron characteristic charging energy is high enough such that it limits the number of electrons that can be accommodated on each particle to one.
• the use of ultra-small particles allows us to attain a larger inner particle oxide thickness for the same particle density. Thicker oxide improves the isolation of particles, hence it limits the lateral leakage further, thus improving the memory of the device.
• the nanoparticle memory can be operated at low voltages compared to conventional flash memory.
• the use of a thin oxide between the particles and the silicon channel allows charging via quantum tunneling instead of hot carrier injection at higher voltages. Direct tunneling is therefore desired in the charging and discharging of the Si particles to prevent hot- carrier degradation.
• lower voltages mean less electrons are accommodated on particles.
• the invention includes a method for converting silicon bulk crystals into individual silicon nanoparticles .
• the silicon nanoparticles may also be combined or reconstituted into crystals, solids, films, etc.
• the method for creating the nanoparticle of the invention is an electrochemical treatment which involves gradually advancing bulk silicon, e.g., a wafer, into a chemical etch bath at a low speed while etching is taking place, in the presence of an external current.
• a meniscus forms as a very thin slice of the silicon that is at the interface of etchant solution and air.
• the slow advance of the silicon creates a large section which is meniscus-like. In effect, a traveling meniscus is created as the silicon material is gradually advanced into the etchant bath while electrical current is applied.
• the process enriches the ultra small substructure of the material. Moreover, it makes the top skin of the silicon material extremely fragile.
• the ultra-small structures which are silicon nanoparticles, may then be separated from the material and recovered.
• a preferred embodiment of the method is illustrated in FIG. 10.
• the preferred embodiment uses a silicon single crystalline wafer 100, a platinum cathode 120 in the form of a sheet or a wire, HF acid, H 2 0 2 liquid, and other chemicals that might include methanol or water for an etchant bath 140.
• the preferred silicon wafers are (100) or (111) oriented, 1-10 ohm-cm resistivity, p-type boron-doped silicon.
• the wafer 100 and the cathode 120 are connected to a constant current source 160 driven by a power source 180.
• the cathode 120 is vertically or horizontally immersed in the etchant.
• the silicon wafer 100 is gradually advanced. By way of example, it has been found that a speed of about 1 mm per hour produces good results.
• a magnetic stirrer 220 ensures that the chemicals of the etchant stay uniformly mixed.
• the meniscus travels along the silicon wafer 100 due to the gradual immersion and etches to create silicon nanoparticle structures on the top skin of the silicon material.
• H 2 0 2 as a catalyst
• significant current a high etching rate is realized which produces films of interconnected substructure with much reduced sizes, approaching the limit of size.
• the lateral anodization creates a high current concentration in the top skin of the silicon wafer 100, hence the high etching rate leading to the ultra-small nanoparticle structures, especially at the meniscus (air—liquid interface).
• Advancing the sample in the etchant slowly and uniformly results in a large area of the sample that is meniscus-like, hence enriching the ultra small nano substructure.
• Nanoparticles are then obtained by separating the silicon wafer 100 from the etchant bath 140, and separating the silicon nanoparticles from the surface of the silicon wafer 100.
• the silicon wafer 100 is first removed from the etchant bath 140 and rinsed with methanol.
• the silicon wafer 100 is then preferably immersed in an ultra sound acetone (ethanol, methanol or any other solvent) bath for a brief period of time.
• the very top layer of the silicon film on the wafer 100 crumbles into ultra small silicon nanoparticles, leaving behind a bottom layer of a deep red luminescent silicon nanoparticle material.
• This colloid is left to settle. Larger yellowish/orangish luminescent particles precipitate in a few hours, leaving behind a bluish luminescent colloid. Residual larger clusters with very low abundancy (1 part in one thousand) may remain in the colloid. Those can be separated by filtering the colloid using a commercial 200 nm filter, resulting in a highly uniform size distribution.
• the colloid is stable as shown by the fact that it retains characteristic emission over weeks, indicating that the silicon nanoparticles are small enough to stay in suspension.
• any method which separates the silicon nanoparticles from the etched anode is suitable, but the solvent with breaking force supplied by ultrasound waves is preferred. Shaking, scraping or banging are exemplary, non-exhaustive, alternative techniques that may be used to break off the particles.
• the ultrasound appears to work best, though. What is left of the silicon wafer 100 can be recycled (used as a source for creating additional nanoparticles) two to three times or even more depending upon its thickness. This cuts the cost of the raw material.
• the silicon nanoparticles of the invention have good electronic, chemical and structural qualities.
• H 2 0 2 as part of the etchant solution to produce the silicon nanoparticles provides a high quality hydrogen coating (termination or passivation), dominated by an ideal stretching mode with no di- or tri hydrides that act as nonradiative electronic traps.
• the high quality coating fully protects the silicon particles from uncontrollable low quality post interactions in the ambient atmosphere that would generate nonradiative traps.
• the preferred etchant leaves no oxygen on the particles.
• the hydrogen coating can be replaced by a high quality oxide coating by post immersion in H 2 0 2 . This is due to the fact that the high quality nature of the hydrogen termination makes it possible for hydrogen to be substituted with an ultra thin high quality oxide termination.

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