Classifications

• • C—CHEMISTRY; METALLURGY
  • C30—CRYSTAL GROWTH
  • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
  • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
  • C30B29/02—Elements
  • C30B29/06—Silicon
• • C—CHEMISTRY; METALLURGY
  • C30—CRYSTAL GROWTH
  • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
  • C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
  • C30B15/02—Single-crystal growth by pulling from a melt, e.g. Czochralski method adding crystallising materials or reactants forming it in situ to the melt
  • C30B15/04—Single-crystal growth by pulling from a melt, e.g. Czochralski method adding crystallising materials or reactants forming it in situ to the melt adding doping materials, e.g. for n-p-junction
• • C—CHEMISTRY; METALLURGY
  • C30—CRYSTAL GROWTH
  • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
  • C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
  • C30B15/20—Controlling or regulating
  • C30B15/206—Controlling or regulating the thermal history of growing the ingot

Definitions

• the present invention relates to processes for manufacturing ingots of semiconductor material. It relates more particularly to a manufacturing method for adjusting the axial electrical resistivity of the ingots.
• the Czochralski process is a technique commonly used to form monocrystalline silicon ingots. It consists in melting in a crucible a quantity of silicon, called charge or mass, and crystallizing the silicon from a monocrystalline seed. The seed, oriented along a crystallographic axis of the crystal to be formed, is first dipped in the molten silicon bath. Then he is rotated and slowly pulled up. Thus, the solid silicon ingot gradually grows by feeding on the bath.
• Silicon is generally doped to adjust its electrical resistivity.
• Dopants such as boron and phosphorus, are incorporated before crystallization, either in the melt or in the feed before the melting step. With the Czochralski drawing process, the dopants tend to accumulate in the molten silicon bath because of the phenomenon of segregation. The zone of the ingot corresponding to the beginning of the solidification has a lower dopant concentration than the end zone of solidification. In other words, the concentration of dopants in the silicon ingot increases as it crystallizes. This results in a variation of the electrical resistivity on the height of the ingot.
• US2007 / 0056504 discloses a technique for forming a silicon ingot having uniform axial resistivity, by maintaining constant dopant concentration in the molten silicon bath.
• the control of the resistivity is obtained by the addition at regular intervals of silicon and dopants in the bath.
• the patent FR2997096 describes a method for correcting the electrical resistivity of a silicon ingot after crystallization, creating thermal donors by annealing.
• Thermal donors are agglomerates created from the interstitial oxygen contained in silicon (ie the oxygen atoms occupy interstitial positions in the crystal lattice), when subjected to a temperature of between 350 ° C and 550 ° C. ° C. Each thermal donor generates two free electrons, which causes a variation in the electrical resistivity of the silicon.
• the lifespan of the charge carriers is not affected by the formation of thermal donors because they are not recombinant.
• This method notably comprises a step of measuring the concentration of interstitial oxygen along the ingot, a step of calculating the concentration of thermal donors to be created in each portion of the ingot to reach a target value of resistivity, a step of calculating the annealing temperature to be applied in each portion of the ingot to generate these thermal donors, and the implementation annealing in an oven comprising zones of different temperatures.
• the temperature gradient within the silicon ingot may be very different from that introduced in the furnace.
• the concentrations of thermal donors generated in the different portions of the ingot do not then correspond to the previously calculated concentrations. For this reason, it is preferable to separate these portions by cutting the ingot and to distribute them in the different temperature zones of the oven. In this way, the desired concentration of thermal donors is thus obtained.
• the aim of the invention is to provide a rapid and economical method for manufacturing semiconductor ingots of predefined axial electrical resistivity.
• axial resistivity of an ingot means resistivity along the longitudinal axis of the ingot. Since the ingot generally has the shape of a cylinder, the longitudinal axis of the ingot may be coincident with the axis of revolution of this cylinder.
• this objective is attained by providing a method for manufacturing ingots of semiconductor material comprising the following steps:
• the temperature of the semiconductor material decreases slowly, for example from 1414 ° C (silicon melting temperature) to room temperature (about 25 ° C). However, between 350 ° C and 550 ° C, the interstitial oxygen contained in the semiconductor material forms thermal donors.
• the process steps relating to the reference ingot are used to determine the formation kinetics of the thermal donors for a given draft recipe, and in particular the duration during which thermal donors have been formed in the reference ingot during crystallization (ie duration during which the temperature of the semiconductor material was between 350 ° C and 550 ° C).
• This duration can be qualified as "effective duration of a thermal donor formation anneal", since the solidification of the semiconductor material (from 550 ° C. to 350 ° C.) produces thermal donors in the same way as annealing. classic.
• the ingots subsequently crystallized following the same drawing recipe will have the same effective duration of formation of the thermal donors.
• ingots having a target profile of axial resistivity can be obtained directly after the draw.
• the axial resistivity can be adjusted to the target profile by varying the amount of thermal donors created in each zone of the ingot during crystallization.
• the amount of thermal donors created is modulated by controlling the amount of oxygen that is incorporated into each zone of the ingot, given the effective duration of thermal donor formation in that area.
• the manufacturing method according to the invention makes it possible to obtain ingots whose axial resistivity has been previously defined, without resorting to a cutting step and to a subsequent annealing step.
• the manufacturing method according to the invention is therefore faster and less expensive to implement than the method of the prior art.
• the target profile of axial resistivity is constant. In other words, it is sought to obtain ingots whose axial resistivity is uniform.
• the method according to the invention may also have one or more of the following characteristics, considered individually or in any technically possible combination:
• the second ingot is subjected to an additional annealing of the formation of the thermal donors for a predetermined duration, the duration of the annealing additional to the effective times when determining the axial profile of the interstitial oxygen concentration;
• the concentration of oxygen in the second molten charge is modulated by dipping into the second molten charge a part comprising at least one segment of a ring disposed around the second ingot, said part being formed of an oxygen-containing material, for example quartz or silica; and
• the method further comprises, when the first and second melts containing dopants, a step of determining an axial profile of the dopant concentration in the second ingot before calculating the concentration values of thermal donors.
• This axial profile of the dopant concentration in the second ingot can be determined by measuring the concentration of dopants in the different zones of the reference ingot, when the first and second melted charges contain dopants in identical concentrations, or be calculated by the law.
• FIG. 1 represents steps S1 to S7 of a method for manufacturing semiconductor ingots according to the invention
• FIG. 2 represents a preferential embodiment of the crystallization step S7 of the second ingot, which makes it possible to increase the concentration of interstitial oxygen in the second ingot;
• FIGS. 3A to 3H illustrate an example of implementation of the manufacturing method according to the invention.
• FIG. 1 is a block diagram showing the various steps S1 to S7 of a method for manufacturing ingots of semiconductor material with a particular profile of axial electrical resistivity.
• the semiconductor material of the ingots is, for example, silicon.
• a first silicon ingot hereinafter called reference ingot, is crystallized from a molten silicon bath.
• This bath which also contains oxygen, is obtained by melting a silicon charge in a crucible.
• Oxygen can come from the crucible, usually quartz or silica, because it partially dissolves under the effect of temperature, and / or silicon charge (i.e., silicon in the solid state).
• the molten silicon bath may contain dopants, for example boron and / or phosphorus. These dopants are introduced into the bath in the form of highly doped powders or silicon wafers before drawing the ingot, or are initially contained in the charge. At the end of the crystallization, the dopants are distributed unequally in the reference ingot, which causes a significant variation in the axial resistivity, for example by a factor of 10 between the two ends of the ingot.
• dopants for example boron and / or phosphorus.
• the Czochralski process can be used to obtain a monocrystalline silicon ingot or the Bridgman process for a multicrystalline silicon ingot.
• the reference ingot is crystallized under specific drawing conditions, adapted to the properties of the load and to the selected drawing technique. These conditions are for example the drawing speed of the ingot, vertically with respect to the crucible, the speed of rotation of the crucible and the speed of rotation of the ingot, for an ingot crystallized according to the Czochralski process.
• the silicon of the reference ingot incorporates interstitial oxygen atoms into its crystal lattice.
• These oxygen atoms give rise to thermal donors (DT) during the cooling of silicon, as long as the silicon temperature is between 350 ° C and 550 ° C.
• the duration during which thermal donors are formed depends on the conditions of drawing, and in particular the draw speed of the ingot. In fact, the higher the pulling speed, the faster the temperature of the solid silicon decreases.
• the amount of oxygen incorporated in the ingot also depends on the conditions of draft, in particular the pressure of the atmosphere in the furnace and the rotational speeds of the crucible and the ingot. Therefore, each print recipe has its own thermal donor formation kinetics.
• Steps S2 to S4 make it possible to characterize the formation kinetics of the thermal donors of the drawing recipe used to crystallize the reference ingot.
• step S2 the interstitial oxygen concentration [O1] i incorporated into the reference ingot is measured in different zones distributed along the reference ingot, ie for different positions on the longitudinal axis of the ingot. This gives an axial (or longitudinal) profile of the interstitial oxygen concentration [Oi] i in the reference ingot.
• interstitial oxygen concentration [Oi] i can be performed by Fourier transform infrared spectroscopy (FTIR) on thick plates (thickness> 2mm) taken from the ingot, perpendicular to the longitudinal axis, and whose surface has been polished.
• the number of measurement zones is advantageously equal to the number of platelets cut in the reference ingot.
• the interstitial oxygen concentration [Oi] i is measured on the entire ingot.
• the concentration [Oi] i can be measured at the scale of the ingot by an infrared spectroscopy technique commonly called "Whole-rod FTIR".
• This technique derived from Fourier transform infrared spectroscopy (FTIR) consists of scanning the ingot with an infrared beam, this beam moving parallel to the longitudinal axis of the ingot. The absorption of the infrared beam by the ingot makes it possible to determine an interstitial oxygen concentration averaged according to the diameter of the ingot.
• FTIR Fourier transform infrared spectroscopy
• the ingot After measuring the initial electrical resistivity in each zone of the reference ingot, the ingot is annealed so as to form thermal donors, in addition to those formed during crystallization.
• the temperature of this annealing is preferably homogeneous and between 350 ° C and 550 ° C.
• the electrical resistivity after annealing is measured in each zone of the reference ingot. Since the variation in resistivity is attributable to the formation of additional thermal donors, it can be deduced from the concentration of thermal donors formed by the annealing.
• the oxygen concentration [Oi] i in each of the measurement zones is determined from the concentration of newly created thermal donors and the annealing time between 350 ° C and 550 ° C.
• step S3 the concentration of thermal donors [DT] i created during the crystallization of the reference ingot is measured along the reference ingot, in the same zones as before.
• the set of measurements constitutes an axial profile of the concentration of thermal donors [DT] i.
• the concentration [DT] i is preferably obtained from the variation of resistivity or from the variation of the charge carrier concentration, caused by annealing at high temperature (> 600 ° C.).
• This annealing at high temperature makes it possible to destroy the thermal donors formed during the crystallization of the reference ingot.
• the electrical resistivity can be measured (before and after destruction annealing) by the four point method, the Van der Pauw method, or derived from the eddy current measurement.
• the charge carrier concentration can be measured by Hall effect or deduced from CV measurements.
• Step S3 can be implemented after step S2 even when the technique of patent FR2964459 is used to measure the interstitial oxygen concentration [Oi] i. In this case, it suffices to consider the initial electrical resistivity (or charge carrier concentration) of the reference ingot, i.e. after crystallization but before the additional thermal donor formation annealing. Step S3 can also be implemented before step S2, in which case there are no more heat donors when annealing between 350 ° C and 550 ° C.
• step S2 for measuring the concentration of interstitial oxygen [Oi] i
• step S3 for measuring the concentration of thermal donors [Oi] i.
• step S4 the effective duration teff of the annealing between 350 ° C and 550 ° C is determined by each measurement zone of the reference ingot during crystallization. This annealing allowed the formation of thermal donors in concentration [DT] i from the oxygen content [Oi] i. The effective duration teff in a zone of the reference ingot can therefore be determined from the values of [Oi] i and [DT], measured in this same zone in steps S2 and S3 respectively.
• the effective duration teff can be calculated using a relation drawn from the article ["Kinetic formation of oxygen thermal donors in silicon", Wijaranakula C.A. et al., Appl. Phys. Lett. 59 (13), pp. 1608, 1991].
• This article describes the kinetics of formation of thermal donors in silicon by annealing at 450 ° C. It is considered that the duration teff is equivalent to the duration of an annealing at 450 ° C that should have been used to obtain a concentration of thermal donors equal to [DT] i, from an oxygen concentration equal to [Oi] i.
• the initial thermal donor concentration [DT] i, the initial interstitial oxygen concentration [Oi] i and the annealing time t at 450 ° C are related by the following relation:
• the duration t thus calculated is a good approximation of the effective duration teff, ie the time that the silicon spent in the range 350-550 ° C during the solidification of the reference ingot.
• the relation (1) above is preferred because the temperature of 450 ° C is the temperature at which the formation kinetics of thermal donors is best known.
• the annealing at 450 ° C has been the subject of numerous studies, because it constitutes a good compromise between the speed of formation of the thermal donors and the maximum concentration obtained.
• the effective duration teff can be determined using abacuses giving the concentration of thermal donors [DT] i as a function of the duration t of the annealing at 450 ° C, for different values of the oxygen concentration [Oi] i.
• the relationship (1) and the abacuses can be adapted, in particular thanks to the teachings of the article ["Effect of oxygen concentration on the kinetics of thermal donor formation in silicon at temperatures between 350 and 500 ° C, Londos CA et al., Appl. Phys. Lett. 62 (13), pp. 1525, 1993].
• This article also describes the kinetics of formation of thermal donors in silicon, but for annealing temperatures of between 350 ° C. and 500 ° C.
• annealing temperatures of between 350 ° C. and 500 ° C.
• an average duration annealing at 450 ° C can be calculated. This average will then be a better indicator of the actual duration teff associated with this area.
• Steps S5 to S7 of the method of FIG. 1 implement this control of the quantity of thermal donors to achieve in a second silicon ingot a target profile of axial resistivity.
• Step S5 of FIG. 1 consists in calculating the values of a target concentration [DT] t g in thermal donors, making it possible to reach the target profile of axial resistivity during the crystallization of the second ingot, taking into account the resistivity basic of this second ingot.
• base resistivity is meant the intrinsic electrical resistivity of silicon, possibly increased by the addition of acceptor and / or donor dopants (excluding thermal donors).
• the target concentration [DT] t g in thermal donors is calculated for portions of the second ingot corresponding to the measuring zones of the reference ingot, that is to say located at the same positions on the longitudinal axis of the ingots.
• the electrical resistivity p in semiconductor materials such as silicon varies according to two parameters, the concentration m in free major charge carriers and the mobility ⁇ of these carriers, which depend on the concentration of thermal donors [DT] present in silicon. Its general expression is:
• NA / D is the total concentration of NA ionizing and / or ND donor ionizing dopants (for example boron and phosphorus, respectively).
• the concentration m of free charge carriers is equal to the net doping (difference of the acceptor and donor dopant concentrations) to which is added (in the case of an n-type doped silicon) or subtracted (in the case of a p-type silicon) twice the concentration of thermal donors [DT] (two electrons generated by thermal donor).
• the mobility of the majority charge carriers in silicon depends on the temperature T of the silicon and the concentration of dopants, donors and / or acceptors. Taking into account the thermal donors (which are "double" donor dopants), the mobility ⁇ (in cm 2 .V “1 .s " 1 ) can be expressed by the following relation: max / 1 ⁇ 2un) ⁇ n
• the mobility ⁇ is always calculated as a function of the conductivity type of the ingot at the end of crystallization, but with a non-zero NA / D value (see relation (3)).
• a target value ptg of resistivity the values of the target concentration [DT] t g are determined which will make it possible to reach the target profile of axial resistivity.
• the set of target values ptg of resistivity associated with the different measurement zones constitutes the target profile of axial resistivity and the set of values of [DT] t g constitutes, by analogy, an axial profile of the concentration of thermal donors to be formed. during crystallization.
• the manufacturing method it is sought to obtain a second silicon ingot of uniform axial resistivity.
• the target profile of axial resistivity is then constant. In other words, the same target value ptg is used for all the zones of the second ingot.
• the concentration of ionized dopants NA / D is advantageously determined along the second ingot before solving equation (2).
• Two methods can be used to determine the axial profile of the NA / D dopant concentration:
• Ncharge is the concentration of dopants added to the semiconductor charge (or contained in the charge)
• k the effective partition coefficient of the acceptor dopant (NA) OR donor (ND) considered
• f the solidified fraction of the ingot ( expressed in% of the total length of the ingot).
• the first method to determine the concentration NA D implies that the first ingot (or ingot of reference) and the second ingot (or subsequent ingot) are doped in the same way, that is to say with the same (s) species (s) chemical (s) and the same concentration (s) in dopants in the load.
• the second method can be used regardless of the doping of the second ingot.
• thermal donors provide electrons ("donor" character)
• the formation of thermal donors during crystallization can only lower the resistivity of an n-doped silicon ingot and increase the resistivity of a p-type doped silicon ingot.
• the axial profile of the interstitial oxygen concentration [Oi] t g required to obtain in the second ingot the axial profile of the target concentration [DT] t g in thermal donors, and thus the profile, is determined.
• the axial profile of the oxygen concentration [Oi] t g comprises several values associated with the zones for which a value of the target concentration [DT] t g in thermal donors and a value of the effective duration teff are available. Preferably, each of these values is calculated using the relation (1) above, from the corresponding value of [DT] t g calculated in step S5 and the corresponding effective duration teff determined in step S4.
• the dopant concentrations of the first ingot and the second ingot may be different. When both of them are less than 2.10 16 cm ⁇ 3 , it is preferable to use the relation (1) of Wijaranakula CA et al., Both for the calculation of the duration teff (reference ingot) and for the determination the interstitial oxygen concentration [Oi] t g (second ingot), because this model is particularly accurate. On the other hand, when one wishes to boost the second ingot to a level beyond 2.10 16 cm ⁇ 3 , the model of Kazumi Wada ("Unified model for training kinetics of oxygen thermal donors in silicon", Physical Review B, Flight .30, N.10, pp.
• a value (or several values) of the interstitial oxygen concentration [Oi] t g calculated in step S6 may be considered too high, either because it is greater than the limit value set by the specifications of the manufacturer of the ingots, either because it is greater than the solubility limit of oxygen in silicon (about 2.10 18 cm -3 ).
• a formation annealing of the thermal donors is advantageously applied to the entire second ingot after crystallization (step S7 described below).
• the effective duration teff of formation of the thermal donors is thus increased by the duration of the annealing in each zone of the second ingot.
• the calculation of the interstitial oxygen concentration values [Oi] t g in step S6 then takes into account the new values of effective duration teff.
• This annealing makes it possible to use lower concentrations of interstitial oxygen in the second ingot while ensuring that the thermal donor concentrations calculated in step S5 are reached.
• the annealing temperature is homogeneous along the second ingot and preferably equal to 450 ° C. Its duration can be from one minute to several hours. If the effective formation time of the thermal donors is estimated at a temperature other than 450 ° C., the annealing after crystallization is carried out at this same temperature.
• step S7 the second ingot is crystallized from a molten silicon bath by following the recipe of the draw used to crystallize the reference ingot, that is to say by adopting the same draw parameters .
• This bath is obtained by melting in a crucible a second silicon charge of mass identical to the first charge of silicon.
• the crucible of the second ingot is identical to that of the first ingot, preferably quartz or silica.
• the second molten silicon charge contains oxygen and possibly dopants.
• most of the oxygen contained in the molten silicon bath escapes into the atmosphere of the crystallization furnace, stirred by flows of inert gas.
• the concentration of interstitial oxygen incorporated in the ingot is a function of the oxygen concentration at the interface between the bath and the ingot. It also depends on the partition coefficient of oxygen, close to unity.
• the oxygen concentration of the bath depends mainly on the draft parameters, the furnace atmosphere and the nature of the crucible.
• step S7 the oxygen concentration of the molten silicon bath is adjusted as the crystallization progresses so as to obtain, in each solidified fraction of the second ingot, an interstitial oxygen concentration corresponding to the axial profile [Oi ] t g determined in step S6.
• Various mechanisms make it possible to control the oxygen concentration of the bath.
• a magnetic field may be generated around the crucible to locally slow the convection of silicon within the bath.
• This magnetic field is usually used to contain oxygen in molten silicon at the periphery of the crucible, thus forming so-called "magnetic-CZ" ingots weakly contaminated with oxygen (because formed from molten silicon in the center of the crucible).
• the magnetic field can instead be configured to homogenize the bath and accelerate the dissolution of the crucible at its periphery, in order to enrich the oxygen bath.
• a crucible (quartz or silica) having a variable depth porosity can be used to vary the dissolution rate of the crucible, and therefore the rate of incorporation of oxygen in the bath.
• the most porous portion of the crucible dissolves more rapidly and thus increases the oxygen content of the bath.
• the bath is enriched more slowly oxygen.
• the control of the speed of rotation of the crucible is another technique for varying the dissolution rate of the crucible. Like the previous techniques, it makes it possible to modulate the oxygen concentration of the bath upwards or downwards.
• the control of the oxygen concentration of the bath can also be obtained by adjusting the flow of inert gas or the pressure of the inert gas in the furnace atmosphere.
• the bath is depleted of oxygen when the flow increases or when the pressure of the gas decreases, since the evaporation of oxygen (in the form of SiO) is favored. Conversely, as the flow decreases or the pressure increases, the oxygen content of the bath increases.
• Another molten charge of silicon may in particular be poured into the crucible of the second ingot during the crystallization step S7.
• This additional charge, placed in a secondary crucible is more or less rich in oxygen than the silicon bath contained in the main crucible (ie the crucible where the second ingot is drawn), depending on whether it is desired to increase or decrease the oxygen concentration of the bath.
• the oxygen concentration of the additional filler can be increased by incorporating quartz / silica chips or by keeping the molten silicon longer, which causes further dissolution of the secondary crucible.
• the Secondary crucible may be formed of graphite rather than quartz / silica.
• the oxygen concentration of the molten silicon bath 20 is modulated by immersing a part 21, preferably quartz or silica, at a variable depth h. in the bath 20.
• the part 21 is mounted in translation relative to the crucible and rotates, preferably, at the same speed and in the same direction as the crucible.
• the part 21 comprises at least one segment of a ring disposed around the second ingot. It can comprise several distinct segments of the same ring or, as illustrated in FIG. 2, be formed of an entire ring.
• the second ingot is symbolized by its longitudinal axis 22.
• the segment (s) of the ring, or the entire ring has a cross section with a point 23, for example a triangle.
• the tip 23 is directed towards the bottom of the crucible, in a direction 24 parallel to the longitudinal axis 22 of the ingot.
• the part 21 does not significantly disturb the convection of the molten silicon in the crucible and the oxygen concentration can be increased gradually.
• the annular shape the radial uniformity of the second ingot is further preserved.
• a section in the form of a triangle, as illustrated in FIG. 2, makes it possible to finely vary the surface of the part 21 in contact with the bath 20, and thus to precisely control the oxygen concentration of the bath.
• triangle 23 the two sides corresponding to the non-planar faces of the ring are of the same length
• the surface of the part 21 in contact with the molten silicon bath 20 is written:
• h is the depth to which the ring 21 is plunged (measured with respect to the surface of the molten silicon bath 20)
• Ri the median diameter of the ring (taken at the center of the base of the isosceles triangle 23), R2 the inside diameter of the ring and at the height of the isosceles triangle 23 (measured parallel to the longitudinal axis 22).
• the dimensions R1, R2 and A of the part 21 are respectively 20 cm, 16 cm and 1 cm.
• the manufacturing method of FIG. 1 makes it possible to obtain ingots having a predetermined axial resistivity in a limited number of steps (steps S5 to S7).
• the ingots manufactured after the reference ingot do not need to be cut or annealed with a temperature gradient.
• the molten charges of silicon used to crystallize the reference ingot and the subsequent ingot (s) contain no dopant. This also facilitates the control of electrical resistivity, which is then based exclusively on the formation of thermal donors.
• n-type ingot B of uniform resistivity and equal to 5 ⁇ .cm.
• This ingot B, as well as the ingot A serving as a reference, are ingots made of monocrystalline silicon (8 inches in diameter) crystallized according to the Czochralski method according to a given drawing recipe (draft pressure equal to 14 Torr, flow rate of argon 60 liters / min, crucible rotation speed equal to 8 revolutions / min and rotation speed of the seed equal to 10 revolutions / min).
• 3A and 3B respectively show the measurements of the concentration of thermal donors [DT] i and the measurements of the interstitial oxygen concentration [Oi] i along the reference ingot A after crystallization. They were obtained in the manner described in patent application FR 3009380, from three series of resistivity measurements interspersed with annealing performed around 450 ° C. and 650 ° C.
• the longitudinal position of the measurement zones is given by the fraction solidified f s of ingot A, on the abscissa in FIGS. 3A and 3B. It is expressed as a percentage of the total length of the ingot.
• the measurement zones are distributed over almost the entire length of the ingot A, being located at 0%, 10%, 20%, 50%, 70%, 80% and 95% of the total length of the ingot A.
• the effective duration teff of annealing at 450 ° C undergone during the crystallization of the ingot A is calculated for each of these longitudinal positions, according to step S4.
• the effective duration values teff obtained are also valid for the ingot B to be manufactured later, since the same drawing recipe and the same amount of load will be used.
• the result of the calculation of the effective duration teff corresponds to the curve 31 of FIG. 3C (curve bearing the caption "without additional annealing").
• FIG. 3D shows the axial profile of the ND concentration in dopants (phosphorus) in ingots A and B, obtained thanks to the Scheil-Gulliver law (k, the partition coefficient of phosphorus is equal to 0.35 ). Knowing for each fraction f s measured the ND dopants content and the resistivity target value (5 ⁇ .cm), the axial profile [DT] t g (fs) of the thermal donor concentration to be generated in the ingot is then determined. B (step S5). This axial profile is shown in FIG. 3E. The curve 32 of FIG.
• 3F (bearing the legend "without additional annealing") represents a first axial profile [Oi] t g (fs) of the interstitial oxygen concentration necessary to obtain the ingot of uniform resistivity B. It has was determined using relation (1), taking for each fraction f s measured the actual duration of annealing at 450 ° C given by curve 31 (Fig.3C, "without additional annealing") and the concentration [ DT] t g thermal donors to generate (Fig.3E).
• the target concentration [Oi] t g in interstitial oxygen is particularly high for the high values of the fraction f s of ingot B, ie for the zones of the ingot solidified last. This is due to the fact that the effective duration tetf is low in these same areas (see Fig.3C).
• a concentration of oxygen can adversely affect the quality of the silicon wafers that will come from the ingot B. It is therefore preferable to opt for an additional annealing at 450 ° C., to be carried out after crystallization of the ingot B. This annealing has the effect of decrease the target concentration [Oi] t g in interstitial oxygen along the ingot B, as can be seen in FIG.
• the second target profile (curve 33, "with additional annealing) of the oxygen concentration [Oi] 3 ⁇ 4 is achieved by quenching in a controlled manner in the molten silicon bath a quartz ring, such as shown in FIG. 2.
• concentration of interstitial oxygen [Oi] i of the ingot A that is to say the concentration of oxygen after drawing when no additional source of oxygen is used
• Figure 3G shows the profile of this additional concentration [Oi] SU pp, expressed as a percentage of the basal concentration [Oi] i.
• FIG. 3G is equivalent to showing the increase of the contact surface S quartz / silicon that must be created by dipping the ring in the bath.
• This increase of the contact area S is, according to the above relationship (5), achieved by varying the ring depth h as shown in FIG. 3H.
• the manufacturing process makes it possible to make the axial electrical resistivity of the ingots uniform by choosing a target profile of constant resistivity. However, it also makes it possible to obtain ingots whose axial resistivity is variable. For example, silicon ingots whose conductivity type changes from p to n during crystallization can be manufactured by the method of FIG.
• the quantity of thermal donors formed during the crystallization can under certain conditions described above (oxygen concentration [Oi] t g and effective duration teff) compensate for the initial doping of the p-type silicon filler.
• the axial resistivity profile then comprises one or a plurality of resistivity peaks corresponding to the change (s) of the conductivity type. This type of ingot finds many applications, for example for the manufacture of photovoltaic cells with high voltage.
• Germanium is a potential candidate because oxygen-based thermal donors are also formed during the crystallization of germanium.

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• Crystals, And After-Treatments Of Crystals (AREA)
• Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)

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• 2015
  • 2015-12-14 FR FR1562311A patent/FR3045074B1/fr active Active
• 2016
  • 2016-12-13 TW TW105141142A patent/TWI746494B/zh not_active IP Right Cessation
  • 2016-12-14 EP EP16819040.3A patent/EP3390699A1/de active Pending
  • 2016-12-14 WO PCT/EP2016/080982 patent/WO2017102832A1/fr active Application Filing
  • 2016-12-14 CN CN201680079742.5A patent/CN108495956B/zh not_active Expired - Fee Related

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